Name: 712-50-5|Cyclohexyl phenyl ketone|98%
Brand: Ambeed
SKU: A233691
Price: 6.0 USD
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1
[ 712-50-5 ]
[ 827-52-1 ]

Reference： [1]Bulletin de la Societe Chimique de France,1936,vol. <5> 3,p. 239,247
Chemisches Zentralblatt,1937,vol. 108,p. 2585

2
[ 712-50-5 ]
[ 4410-75-7 ]

Yield	Reaction Conditions	Operation in experiment
88%	With chlorobenzene In methanol at 20℃; for 9h; Sealed tube; Green chemistry; chemoselective reaction;
85%	With potassium hydroxide; hydrazine hydrate monohydrate In diethylene glycol 1.) reflux, 1.5, 2.) 195 deg C, 4 h;
79%	With manganese powder; nickel(II) chloride ethylene glycol dimethyl ether complex; 1,1,3,3-Tetramethyldisiloxane; potassium-t-butoxide; N,N′-dicyclohexylimidazolium tetrafluoroborate In toluene at 70℃; for 5h;

78%	With phosphonic Acid; iodine In benzene at 120℃; for 24h; Sealed tube; Inert atmosphere;	4.2. Typical procedure for preparation of targeted molecules General procedure: Under N2, a mixture of aromatic ketone 1 (0.6 mmol), H3PO3 (147.6 mg, 1.8 mmol), I2 (76.2 mg, 0.3 mmol) and benzene (1.2 mL) was stirred in a 25 mL closed sealed tube in oil bath at 80°C for indicated time. After the mixture was cooled down to the room temperature, the mixture was quenched by Na2S2O3 aqueous solution and was extracted with EtOAc three times. Then the combined the organic layer was dried over MgSO4 and filtrated. The filtrate was concentrated and the residue was further purified by column chromatography on silica gel to give the product 2.
	With Pd-BaSO₄ Hydrogenation;
	With hydrogenchloride; zinc,^6a mercury,^6b
	With potassium hydroxide; hydrazine In diethylene glycol
265 mg	With triethylsilane; trifluoroacetic acid for 18h; Ambient temperature;
	With triethylsilane; [Fe(η⁵-C₅H₄PFPh₂)₂][B(C₆F₅)₄]₂ In dichloromethane-d2 at 25℃; for 96h; Glovebox; Inert atmosphere; Schlenk technique;
12.7 %Spectr.	With hydrogen In hexane at 100℃; for 24h;
97 %Spectr.	With triethylsilane; 2C₂₄BF₂₀^(1-)*C₂₁H₁₆N₃P⁽²⁺⁾ In dichloromethane at 20℃; for 1.5h; Inert atmosphere;
	With triethylsilane; tetracarbonylbis(μ-chloro)dirhodium(I) In dichloromethane at 0 - 20℃; for 24h; Inert atmosphere;

Reference： [1]Volkov, Alexey; Gustafson, Karl P. J.; Tai, Cheuk-Wai; Verho, Oscar; Bäckvall, Jan-E.; Adolfsson, Hans [Angewandte Chemie - International Edition, 2015, vol. 54, # 17, p. 5122 - 5126][Angew. Chem., 2015, vol. 54, # 17, p. 5211 - 5215,5]
[2]Hartmann; Batzl [European Journal of Medicinal Chemistry, 1992, vol. 27, # 5, p. 537 - 544]
[3]Cook, Adam; MacLean, Haydn; St. Onge, Piers; Newman, Stephen G. [ACS Catalysis, 2021, vol. 11, # 21, p. 13337 - 13347]
[4]Deng, Jinfeng; Xiao, Jing; Wang, Xiaoyi; Luo, Huang; Jia, Zhicheng; Wang, Jie [Tetrahedron, 2022, vol. 113]
[5]Rosenmund et al. [Chemische Berichte, 1959, vol. 92, p. 494,499]
[6]Ssidorowa; Zukerwanik [Zhurnal Obshchei Khimii, 1940, vol. 10, p. 2073,2075][Chemisches Zentralblatt, 1941, vol. 112, # I, p. 2930]
[7]Davies,K.M.; Hickinbottom,W.J. [Journal of the Chemical Society, 1963, p. 373 - 378]
[8]Savino, T. G.; Kanakarajan, K.; Platz, M. S. [Journal of Organic Chemistry, 1986, vol. 51, # 8, p. 1305 - 1309]
[9]Mallov, Ian; Stephan, Douglas W. [Dalton Transactions, 2016, vol. 45, # 13, p. 5568 - 5574]
[10]Tian, Chengcheng; Zhu, Xiang; Abney, Carter W.; Tian, Ziqi; Jiang, De-En; Han, Kee Sung; Mahurin, Shannon M.; Washton, Nancy M.; Dai, Sheng [Chemical Communications, 2016, vol. 52, # 80, p. 11919 - 11922]
[11]Andrews, Ryan J.; Chitnis, Saurabh S.; Stephan, Douglas W. [Chemical Communications, 2019, vol. 55, # 39, p. 5599 - 5602]
[12]Argouarch, Gilles [New Journal of Chemistry, 2019, vol. 43, # 28, p. 11041 - 11044]

3
[ 712-50-5 ]
[ 7500-66-5 ]

Yield	Reaction Conditions	Operation in experiment
92%	With hydrogen bromide; dimethyl sulfoxide In water; ethyl acetate at 60℃; for 6h;
92%	With Oxalyl bromide; dimethyl sulfoxide In dichloromethane at -10 - 40℃; for 1h; Inert atmosphere;	Bromination of Alkenes, Alkynes and Ketones; General Procedure General procedure: To a solution of (COBr)2 (0.43 mL, 3.0 mmol, 1.5 equiv) in CH2Cl2 (10mL) at -10 °C was added dropwise a solution of DMSO (0.21 mL, 3.0mmol, 1.5 equiv) in CH2Cl2 (10 mL) under an atmosphere of nitrogen. After 10 min, a solution of alkene, alkyne or ketone (2 mmol, 1.0 equiv) in CH2Cl2 (5 mL) was added. The mixture was then allowed to warm to 20-40 °C and stirred for 0.5-3 h. Distilled H2O (20 mL) was added dropwise at 0 °C. After stirring for 10 min, the organic layer was separated and washed with brine (2 × 20 mL), dried (Na2SO4), filtered and concentrated under vacuum to afford the brominated product. Most products can be obtained in high purity without further purification, except 3n, 7d, and 7f. The three products need purification by flash chromatography (silica gel, PE/EtOAc = 10:1 for 3n, PE/EtOAc= 60:1 for 7d, PE/EtOAc = 20:1 for 7f).
	With bromine In water; acetic acid at 25℃; stereoelectronic effects;

	With bromine
	With sodium hypochlorite; hydrogen bromide In water at 60 - 100℃; for 2.5h;	4.b; G 18.7g of NaCIO 12% (34.8mmoles) were added at 6O0C in 30' to a stirred dispersion of 4.71 g of cyclohexyl-phenylketone (25mmoles) in 1 1.52g of hydrobromic acid 48% (68.3 mmoles). The mixture was then heated from 60° to 1000C in two hours. After cooling at 7O0C the organic phase was separated and washed with 5Og of a 10% water solution of sodium sulfite, then with 5Og of water. The organic phase (6.6g) was used without purification for the next step.Hl NMR(300MHz, CDCb): δ: 8.02-8.12 (d,2H); 7.38-7.60 (m,3H); 2.27-2.42 (m,2H); 2.10- 2.25 (m,2H); 1.75-1 .90 (m,2H); 1.47-1 .65 (m,3H); 1.35-1.46 (ml H).
	With sodium hypochlorite; hydrogen bromide In water at 60 - 100℃; for 2.5h;	4.b; G b) Halogenation Synthesis of 1-bromo-cyclohexyl-phenylketone (Method G). 18.7 g of NaClO 12% (34.8 mmoles) were added at 60° C. in 30' to a stirred dispersion of 4.71 g of cyclohexyl-phenylketone (25 mmoles) in 11.52 g of hydrobromic acid 48% (68.3 mmoles). The mixture was then heated from 60° to 100° C. in two hours. After cooling at 70° C. the organic phase was separated and washed with 50 g of a 10% water solution of sodium sulfite, then with 50 g of water. The organic phase (6.6 g) was used without purification for the next step. H1NMR(300 MHz, CDCl3): δ: 8.02-8.12 (d,2H); 7.38-7.60 (m,3H); 2.27-2.42 (m,2H); 2.10-2.25 (m,2H); 1.75-1.90 (m,2H); 1.47-1.65 (m,3H); 1.35-1.46 (m,1H). Synthesis of 1-chloro-cyclohexyl-phenylketone (Method B).
	With bromine; acetic acid Inert atmosphere; Reflux;	General Procedure B: Preparation of Bromohyrins 4l-4q⁴ General procedure: Bromine (7.5mmol) was added dropwise to a solution of ketone (5 mmol) prepared from the acylation of F-K reaction in 20 ml AcOH. The solution was heated under reflux until convocation was completed. After the reaction was cooled, the solution was poured into cracked ice and 15 ml dilute NaOH was added, then extracted with EtOAc (3×20 mL). After washing with water, the organic extract was dried with NaSO4 and concentrated in vaco, the residue was purified by column chromatography to afford α-Bromo ketones. To a solution of α-Bromo ketone (5 mmol) in CH3OH, Sodium borohydride (5.5mmol) was added slowly at 0°C. The solution was allowed to stir at 0°C until TLC indicated complete consumption of the starting α-Bromo ketones. The reaction mixture was quenched by saturated aqueous ammonium chloride solution and extracted with ethyl acetate (3×10 mL). The combined organic layers were washed with brine and then dried over anhydrous magnesium sulfate, and concentrated in vacuo to provide the crude products, which were purified by column chromatograph packed with silica gel using petroleum ether/ethyl acetate (50:1 to 10:1) to afford the pure products.
	With pyridinium hydrobromide perbromide; acetic acid at 20℃; for 10h; Schlenk technique;
	With bromine In tetrachloromethane at 20℃; for 2h; Inert atmosphere;
	With bromine; acetic acid In dichloromethane at 20℃; for 12h;
	With bromine In tetrachloromethane at 20℃; for 2h; Inert atmosphere;
	With hydrogen bromide; dimethyl sulfoxide In water; ethyl acetate at 60℃;

Reference： [1]Song, Song; Li, Xinwei; Sun, Xiang; Yuan, Yizhi; Jiao, Ning [Green Chemistry, 2015, vol. 17, # 6, p. 3285 - 3289]
[2]Ding, Rui; Li, Jiaqi; Jiao, Wenyi; Han, Mengru; Liu, Yongguo; Tian, Hongyu; Sun, Baoguo [Synthesis, 2018, vol. 50, # 21, p. 4325 - 4335]
[3]Pollack, Ralph M.; Kayser, Robert H.; Cashen, Michael J. [Journal of Organic Chemistry, 1984, vol. 49, # 21, p. 3983 - 3987]
[4]Stevens; Farkas [Journal of the American Chemical Society, 1952, vol. 74, p. 618] Wasserman; Gorbunoff [Journal of the American Chemical Society, 1958, vol. 80, p. 4568,4570]
[5]Current Patent Assignee: LAMBERTI S.P.A. - WO2009/135895, 2009, A1 Location in patent: Page/Page column 17
[6]Current Patent Assignee: LAMBERTI S.P.A. - US2011/65962, 2011, A1 Location in patent: Page/Page column 5
[7]Wang, Zhihui; Li, Meiyi; Zhang, Wenqin; Jia, Jiangnan; Wang, Fei; Xue, Song [Tetrahedron Letters, 2011, vol. 52, # 45, p. 5968 - 5971]
[8]Chen, Wenxin; Liu, Zheng; Tian, Jiaqi; Li, Jin; Ma, Jing; Cheng, Xu; Li, Guigen [Journal of the American Chemical Society, 2016, vol. 138, # 38, p. 12312 - 12315]
[9]Jarava-Barrera, Carlos; Parra, Alejandro; Amenós, Laura; Arroyo, Ana; Tortosa, Mariola [Chemistry - A European Journal, 2017, vol. 23, # 69, p. 17478 - 17481]
[10]Yang, Tonghao; Fan, Xing; Zhao, Xiaopeng; Yu, Wei [Organic Letters, 2018, vol. 20, # 7, p. 1875 - 1879]
[11]Gonzalez, Maria J.; Gonzalez, Jesus; Vicente, Ruben [European Journal of Organic Chemistry, 2012, # 31, p. 6140 - 6143,4]
[12]Ren, Xinyi; Shen, Chaoren; Wang, Guangzhu; Shi, Zhanglin; Tian, Xinxin; Dong, Kaiwu [Organic Letters, 2021, vol. 23, # 7, p. 2527 - 2532]

4
[ 712-50-5 ]
[ 1135-71-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sulfuryl dichloride
	With sulfuryl dichloride Heating;
	With hydrogenchloride; calcium hypochlorite In water at 60℃; for 1.5h;	4.b; B 4.01 g of Ca (CIOJ2 65% (18.2 mmoles) were added in 60' to a pressure vessel containing 1.88g of cyclohexyl-phenylketone (l Ommoles) dispersed at 6O0C in 4.96g of HCI 37% (50mmoles). After 30' under stirring at 6O0C the organic phase was separated and washed with 10ml of water obtaining 1Og of an oil. The oil was used without purification for the next step (2.3g).Hl NMR(300MHz, CDCb): δ: 8.05-8.15 (d,2H); 7.38-7.60 (m,3H); 2.07-2.30 (m,4H); 1.75- 1.90 (m,2H); 1.50-1 .67 (m,3H); 1.25-1 .4 (m,l H).

	With hydrogenchloride; calcium hypochlorite In water at 60℃; for 1.5h;	4.b; B 4.01 g of Ca (ClO)2 65% (18.2 mmoles) were added in 60' to a pressure vessel containing 1.88 g of cyclohexyl-phenylketone (10 mmoles) dispersed at 60° C. in 4.96 g of HCl 37% (50 mmoles). After 30' under stirring at 60° C. the organic phase was separated and washed with 10 ml of water obtaining 10 g of an oil. The oil was used without purification for the next step (2.3 g). H1NMR(300 MHz, CDCl3): δ: 8.05-8.15 (d,2H); 7.38-7.60 (m,3H); 2.07-2.30 (m,4H); 1.75-1.90 (m,2H); 1.50-1.67 (m,3H); 1.25-1.4 (m,1H).
	With hydrogenchloride; dihydrogen peroxide In water at 45 - 50℃; for 1h; Molecular sieve;	1-2 (A) 85.8 g (content 92%, 0.42 mol), 75 g 1,1-dichloroethane, 0.5 g L-potassium molecular sieve and 300 g (23%) hydrochloric acid aqueous solution (B) were placed in a 500 ml four-necked flask equipped with a stirrer. the temperature was raised to about 45 ° C, and 140 g of 30% hydrogen peroxide was added dropwise. The reaction was maintained at 45-50 ° C. The reaction was followed by chromatography, and the temperature was kept at 50 ° C for 1 hour, After the end of the reaction, the temperature was controlled to 57-60° C, 33% sodium hydroxide solution was slowly added dropwise for 4 hours. After the addition was completed, the temperature was maintained at 57-60 ° C for 5 hours. After the reaction, the mixture was allowed to stand for stratification, and the lower organic phase was separated. After cooling, the crystals were cooled to give a crude product (yield: 84 g), and then recrystallized from petroleum ether to give 73.12 g white crystals (content: 99.58 %. 0.356 mol). The molar yield was 84.8%.
	With chlorine In dichloromethane at 55 - 60℃; for 0.333333h; Irradiation;	2 Example 2: Preparation of 1-hydroxycyclohexyl phenyl ketone The dichloroethane solution of cyclohexyl phenyl ketone (the mass ratio of cyclohexyl phenyl ketone and dichloroethane is 1:1) is pumped into a micro mixer with a channel inner diameter of 800 μm to adjust the cyclohexyl phenyl ketone The flow rate is 3mol/h, and chlorine is pumped in at the same time. Adjust the flow rate of chlorine to 3.18 mol/h. The ratio of cyclohexyl phenyl ketone and chlorine is 1:1.06. The reaction mixture is mixed in the mixer, and the reaction mixture enters the microchannel reactor with an inner diameter of 800μm for reaction. The system pressure is 1-2atm, the temperature of the constant temperature water bath is 55-60 degrees, and the reaction time is 20min. After the end, sampling is carried out for gas phase analysis. The reaction selectivity is 99.5%. The product is directly used in the next hydrolysis without purification. The exhaust gas treatment method is the same as in Example 1.
17.8 g	With chlorine at 70℃; for 1.5h;	1-3 Add 15g of cyclohexyl benzophenone to the reactor with condenser,Chlorine gas was introduced for reaction at 70°C for 1.5 hours to obtain 17.8 g of compound 1-chlorocyclohexyl benzophenone.The purity of the liquid phase is 98%+, then 15ml of aqueous solution containing 5g of sodium hydroxide is added,0.12g of tetrabutylammonium bromide was reacted at 90°C for about 4.5h, and then separated,After cooling, 16.05 g of 1-hydroxycyclohexyl phenyl ketone was obtained as a brown-yellow solid.The yield based on 1-chlorocyclohexyl benzophenone is 99%, and the liquid phase purity is 96%+.
	With chlorine at 160℃; for 0.116667h; Flow reactor;	13-24 General procedure: (1) Friedel-Crafts reaction section 100: The acyl chloride, aluminum trichloride and the solvent required for Friedel-Crafts reaction are evenly mixed and placed in the first storage tank 1, benzene is placed in the second storage tank 2, and the first feeding pump P1 and The second feeding pump P2 adjusts the feed molar ratio of the flow control reactant, enters the micromixer 3 for mixing, and then enters the first microchannel reactor 4 to perform Friedel-Crafts reaction;(2) Friedel-Crafts reaction intermediate purification section 200: After the material stays in the first microchannel reactor 4 for a certain period of time, it enters the first gas-liquid separation tank 5 to separate hydrogen chloride gas, and absorbs hydrogen chloride tail gas with water to obtain hydrochloric acid; Friedel-Crafts reaction liquid (The first reaction liquid) After accumulating a certain amount in the first gas-liquid separation tank 5, it enters the quenching tank 7. The required hydrochloric acid is placed in the hydrochloric acid storage tank 6, and the metered hydrochloric acid is added by the third feeding pump P3, and under stirring For quenching, the heat generated by the circulating medium in the jacket is taken away, and the temperature of the quenching process is controlled. After the quenching is completed, let it stand for phase separation, take the organic phase GC to detect the conversion rate, and the water phase enters the waste acid tank 8 , The organic phase is in the Friedel-Crafts reaction liquid storage tank 9, and the fourth feeding pump P4 enters the first thin film evaporator 10 to separate the solvent and excess benzene, and the obtained Friedel-Crafts reaction intermediate enters the Friedel-Crafts reaction intermediate storage tank 11 , Excess benzene and recovered solvent enter the recovery solvent and benzene storage tank 12;(3) Chlorination reaction section 300: Friedel-Crafts reaction intermediates are fed into the micromixer 14 from the fifth feeding pump P5 to mix with the chlorine from the chlorine storage tank 13, adjust the chlorine inlet and outlet valves, control the chlorine flow and reaction pressure, and enter the first The chlorination reaction is carried out in the two microchannel reactor 15. The material stays in the second microchannel reactor 15 for a certain period of time and then enters the second gas-liquid separation tank 16 to separate the gas and the second reaction liquid, and sample the GC to detect the conversion rate. Alkaline solution absorbs exhaust gas;(4) Hydrolysis reaction section 400: The sodium hydroxide solution and phase transfer catalyst required for the hydrolysis reaction section are mixed and uniformly placed in the third storage tank 17, fed by the sixth feeding pump P6, and the chlorination reaction intermediate is fed by the seventh The pump P7 feeds materials, enters the micromixer 18 for mixing, and then enters the third microchannel reactor 19 for a certain period of time and then enters the buffer tank 20;(5) Product purification section 500: After a certain amount of material is accumulated in the buffer tank 20, it enters the phase separation tank 21 to stand for phase separation, and the excess sodium hydroxide is neutralized with the hydrochloric acid obtained in step (1), and the water phase enters the waste water tank 22 , The organic phase enters the crude product storage tank 23, the feed pump P8 is added to the second thin film evaporator 24 to distill and purify the finished product into the product storage tank 26, the reboiler enters the reboiler storage tank 25, and the purity of the finished product is detected by GC.

Reference： [1]Tchoubar; Sackur [Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1939, vol. 208, p. 1020]
[2]Rouzaud,J. et al. [Bulletin de la Societe Chimique de France, 1964, p. 2908 - 2916]
[3]Current Patent Assignee: LAMBERTI S.P.A. - WO2009/135895, 2009, A1 Location in patent: Page/Page column 18
[4]Current Patent Assignee: LAMBERTI S.P.A. - US2011/65962, 2011, A1 Location in patent: Page/Page column 5-6
[5]Current Patent Assignee: JIANGSU YOUPU BIOCHEMICAL TECH - CN108299172, 2018, A Location in patent: Paragraph 0015; 0017; 0018; 0020
[6]Current Patent Assignee: TIANJIN JIURI NEW MATERIALS COMPANY LIMITED - CN111056934, 2020, A Location in patent: Paragraph 0024; 0030
[7]Current Patent Assignee: UNIVERSITY OF SCIENCE AND TECHNOLOGY LIAONING - CN111960934, 2020, A Location in patent: Paragraph 0023-0028
[8]Current Patent Assignee: CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD. - CN113493372, 2021, A Location in patent: Paragraph 0074-0105

5
[ 945-49-3 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	With tert.-butylnitrite; oxygen; acetic acid In toluene at 50℃; for 4h;
97%	With dimethyl sulfoxide; triethylamine In dichloromethane at -40 - 20℃; for 8h;
95%	With iodic acid In N,N-dimethyl-formamide at 60℃; for 8h; Inert atmosphere;	32 4.1.1 Typical experimental procedure with HIO₃ (Method A) General procedure: To a solution of p-bromobenzyl alcohol I-1 (187 mg, 1.0 mmol) in DMF (2.0 mL) was added HIO3 (194 mg, 1.1 mmol). The mixture was stirred at 60 °C for 2 h under an Ar atmosphere. After the reaction, the reaction mixture was poured into aq Na2S2O3, and extracted with a mixture of Et2O: hexane=1:1 (3*10 mL). The organic layer was dried over Na2SO4. After being filtration and removal of the solvent under reduced pressure, the residue was purified by flash short column chromatography on silica gel (EtOAc-hexane, 1:4) to give p-bromobenzaldehyde II-1 in 95% yield.

95%	With oxone; C₁₈H₁₇IN₂O₇PolS^(1-)*Na⁽¹⁺⁾; tetra(n-butyl)ammonium hydrogensulfate In acetonitrile at 70℃; for 18h; Sealed tube; Green chemistry;
94%	With Langlois reagent In acetonitrile at 25℃; for 12h; Irradiation; Sealed tube;
94%	With oxygen; C₂₆H₂₁BrO In dichloromethane for 12h; Irradiation;
90%	With 1H-imidazole; tert.-butylhydroperoxide; [(N,N′-bis(3,5-di-chloro-salicylidene)-2,3-diiminopyridine)(acetato)]manganese(III) In acetonitrile at 55℃; for 12h;
88%	With bromopentacarbonylmanganese(I); N-methyl-N,N-di(2-pyridylmethyl)amine; acetone; sodium t-butanolate In toluene at 90℃; for 24h; Inert atmosphere; Schlenk technique; Darkness;
86%	With N-Bromosuccinimide; 1,3-bis(3,5-bis(trifluoro-ethyl)phenyl)thiourea In dichloromethane at 0℃; for 48h; Inert atmosphere;
86%	With dimanganese decacarbonyl In toluene at 120℃; Sealed tube;
84%	With chlorine-triphenylphosphine; dimethyl sulfoxide; triethylamine In dichloromethane at -78 - 20℃; for 3.25h;
83%	With 1H-imidazole; tert.-butylhydroperoxide; [(R,R)-N,N’-bis(3,5-di-chlorosalicylidene)-1,2-cyclohexanediaminato](acetato) manganese(III) In acetonitrile at 20℃; for 12h;	5.1.7 Catalytic runs General procedure: The Mn catalyst (0.25% mol) and imidazol were added to 1.0mL of CH3CN, under stirring. After 10min, the substrate (1.0mmol) and TBHP (4.0mmol, in 2.0mL CH3CN) were added to the reaction flask. After 12h stirring at room temperature, the reaction mixture was filtered and analyzed by GLC using anisole as internal standard.
81%	With magnesium sulphate; vanadyl(IV) sulphate pentahydrate; 4-nitrophenyl(phenyl)methanol; 4,4'-di-tert-butyl-2,2'-bipyridine In water at 0 - 90℃; for 120h;	4.6 Oxidation of alcohols under open-air atmosphere General procedure: VOSO4·5H2O (126.5 mg, 0.5 mmol), 4,4′-di-tert-butyl-2,2′-bipyridyl (268.4 mg, 1 mmol), and p-nitrobenzhydrol (229.3 mg, 0.05 mmol) were placed in a 100 mL round-bottomed flask, and then water (50 mL) was added. Next, the mixture was stirred, and then anhydrous MgSO4 (18.06 g, 150 mmol) was slowly added into the mixture (cooling by ice water). After that, substrate (10 mmol) was added into the mixture at room temperature, and the mixture was stirred at 90 °C for the appropriate time under open-air atmosphere. After the reaction, the mixture was extracted with ethyl acetate and dried over anhydrous MgSO4. The extracts were concentrated in vacuo. Purification of the products was carried out by silica gel column chromatography using hexane and diethyl ether as eluent to afford the analytically pure ketones. In Table 7 (entries 3, 7, and 8), crude products were purified by recrystallization with ethyl acetate in refrigerator, afforded analytically pure ketones. The product was identified by comparison with the commercially available sample using 1H NMR spectroscopy.
	With sodium dichromate; sulfuric acid
	With chromic acid
92 % Chromat.	With phosphotungstate catalyst; dihydrogen peroxide; 1-butyl-3-methylimidazolium Tetrafluoroborate for 3h; Heating;
	With jones reagent
96 %Chromat.	With tert.-butylnitrite; oxygen In water at 50℃; for 24h;
77 %Spectr.	With oxovanadium(IV) sulfate; 4-nitrophenyl(phenyl)methanol; oxygen; magnesium sulfate; 4,4'-di-tert-butyl-2,2'-bipyridine In water at 90℃; for 23h;
6 %Spectr.	With V2O2(μ-MeO)2(μ-WO4)2(4,4'-tBubpy)2; dihydrogen peroxide In water at 90℃; for 24h;
72 %Chromat.	With oxygen; potassium carbonate In water at 40℃; for 24h;
> 99 %Chromat.	With potassium peroxymonosulfate; C₇₂H₅₈IN₁₂O₆Ru₂ In dichloromethane; water at 40℃; for 4h;
> 99 %Chromat.	With oxygen In water at 90℃; for 20h; Green chemistry;
90 %Chromat.	With potassium carbonate In water at 80℃;
92 %Chromat.	With tert.-butylnitrite; oxygen; acetic acid In toluene at 50℃; for 5h;
68 %Spectr.	With [VO(ReO₄)(4,4'-di-tert-butyl-2,2'-bipyridine)2][0.25SO₄*0.5ReO₄]; oxygen In tetrahydrofuran; acetonitrile at 60℃; for 96h; Schlenk technique; chemoselective reaction;	General procedure: General procedure: V1 (27.6 mg, 0.028 mmol) and substrate (0.5 mmol) were placed in a 20mL schlenk flask, and then the mixed MeCN/THF (1:1) solvent (3 mL) was added. The mixture was stirred at 60 C for an appropriate time under O2(balloon) or atmospheric air. After the reaction was completed, Et2O was added tothe reaction mixture. The resulting suspension was filtered and rinsed with Et2O. The combined filtrate was concentrated in vacuo. The yield of the oxidation products was confirmed by 1H NMR spectroscopy using 1,2-diphenylethane or 1,3,5-trimethoxybenzene as the internal standard. Purification of 2a-2c was performed by silica gel chromatography using hexane and EtOAc as the eluent to afford the analytically pure ketones. The isolated products were identified by comparing their 1H NMR spectra with those of authentic samples.
	With oxygen; 1-(tert-butylsulfonyl)-2-iodylbenzene at 70℃; for 14h;
	With oxygen; potassium carbonate In toluene at 60℃; for 14h;

Reference： [1]Karimi, Babak; Vahdati, Saleh; Vali, Hojatollah [RSC Advances, 2016, vol. 6, # 68, p. 63717 - 63723]
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[3]Imai, Sho; Togo, Hideo [Tetrahedron, 2016, vol. 72, # 44, p. 6948 - 6954]
[4]Ballaschk, Frederic; Kirsch, Stefan F. [Green Chemistry, 2019, vol. 21, # 21, p. 5896 - 5903]
[5]Zhu, Xianjin; Liu, Can; Liu, Yong; Yang, Haijun; Fu, Hua [Chemical Communications, 2020, vol. 56, # 82, p. 12443 - 12446]
[6]Uraguchi, Daisuke; Kato, Kohsuke; Ooi, Takashi [Chemical Science, 2021, vol. 12, # 8, p. 2778 - 2783]
[7]Neshat, Abdollah; Kakavand, Meysam; Osanlou, Farzane; Mastrorilli, Piero; Schingaro, Emanuela; Mesto, Ernesto; Todisco, Stefano [European Journal of Inorganic Chemistry, 2020, vol. 2020, # 5, p. 480 - 490]
[8]Budweg, Svenja; Junge, Kathrin; Beller, Matthias [Chemical Communications, 2019, vol. 55, # 94, p. 14143 - 14146]
[9]Location in patent: experimental part Tripathi, Chandra Bhushan; Mukherjee, Santanu [Journal of Organic Chemistry, 2012, vol. 77, # 3, p. 1592 - 1598]
[10]Meng, Shan-Shui; Lin, Li-Rong; Luo, Xiang; Lv, Hao-Jun; Zhao, Jun-Ling; Chan, Albert S. C. [Green Chemistry, 2019, vol. 21, # 22, p. 6187 - 6193]
[11]Bisai, Alakesh; Chandrasekhar; Singh, Vinod K. [Tetrahedron Letters, 2002, vol. 43, # 46, p. 8355 - 8357]
[12]Kakavand, Meysam; Mastrorilli, Piero; Mesto, Ernesto; Neshat, Abdollah; Osanlou, Farzane; Schingaro, Emanuela; Todisco, Stefano [Polyhedron, 2021, vol. 193]
[13]Marui, Kuniaki; Higashiura, Yuuki; Kodama, Shintaro; Hashidate, Suguru; Nomoto, Akihiro; Yano, Shigenobu; Ueshima, Michio; Ogawa, Akiya [Tetrahedron, 2014, vol. 70, # 14, p. 2431 - 2438]
[14]Ssidorowa; Zukerwanik [Zhurnal Obshchei Khimii, 1940, vol. 10, p. 2073,2075][Chemisches Zentralblatt, 1941, vol. 112, # I, p. 2930] Faworsski [Bulletin de la Societe Chimique de France, 1936, vol. <5> 3, p. 239,247][Chemisches Zentralblatt, 1937, vol. 108, # I, p. 2585]
[15]Sabatier; Mailhe [Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1904, vol. 139, p. 344][Bulletin de la Societe Chimique de France, 1905, vol. <3> 33, p. 78]
[16]Chhikara, Bhupender S.; Chandra, Ramesh; Tandon, Vibha [Journal of Catalysis, 2005, vol. 230, # 2, p. 436 - 439]
[17]Stratakis, Manolis; Raptis, Christos; Sofikiti, Nikoletta; Tsangarakis, Constantinos; Kosmas, Giannis; Zaravinos, Ioannis-Panagiotis; Kalaitzakis, Dimitris; Stavroulakis, Dimitris; Baskakis, Constantinos; Stathoulopoulou, Aggeliki [Tetrahedron, 2006, vol. 62, # 46, p. 10623 - 10632]
[18]Karimi, Babak; Farhangi, Elham [Chemistry - A European Journal, 2011, vol. 17, # 22, p. 6056 - 6060]
[19]Kodama, Shintaro; Hashidate, Suguru; Nomoto, Akihiro; Yano, Shigenobu; Ueshima, Michio; Ogawa, Akiya [Chemistry Letters, 2011, vol. 40, # 5, p. 495 - 497]
[20]Location in patent: experimental part Kodama, Shintaro; Nomoto, Akihiro; Yano, Shigenobu; Ueshima, Michio; Ogawa, Akiya [Inorganic Chemistry, 2011, vol. 50, # 20, p. 9942 - 9947]
[21]Karimi, Babak; Behzadnia, Hesam; Bostina, Mihnea; Vali, Hojatollah [Chemistry - A European Journal, 2012, vol. 18, # 28, p. 8634 - 8640]
[22]Verho, Oscar; Dilenstam, Marléne D. V.; Kärkäs, Markus D.; Johnston, Eric V.; Åkermark, Torbjörn; Bäckvall, Jan-E.; Åkermark, Björn [Chemistry - A European Journal, 2012, vol. 18, # 52, p. 16947 - 16954]
[23]Karimi, Babak; Naderi, Zahra; Khorasani, Mojtaba; Mirzaei, Hamid M.; Vali, Hojatollah [ChemCatChem, 2016, vol. 8, # 5, p. 906 - 910]
[24]Vessally, Esmail; Ghasemisarabbadeih, Mostafa; Ekhteyari, Zeynab; Hosseinzadeh-Khanmiri, Rahim; Ghorbani-Kalhor, Ebrahim; Ejlali, Ladan [RSC Advances, 2016, vol. 6, # 108, p. 106769 - 106777]
[25]Karimi, Babak; Farhangi, Elham; Vali, Hojatollah; Vahdati, Saleh [ChemSusChem, 2014, vol. 7, # 9, p. 2735 - 2741]
[26]Kobayashi, Daiki; Kodama, Shintaro; Ishii, Youichi [Tetrahedron Letters, 2017, vol. 58, # 33, p. 3306 - 3310]
[27]Maity, Asim; Hyun, Sung-Min; Wortman, Alan K.; Powers, David C. [Angewandte Chemie - International Edition, 2018, vol. 57, # 24, p. 7205 - 7209][Angew. Chem., 2018, vol. 130, p. 7323 - 7327,5]
[28]Bigdeli, Akram; Karimi, Babak; Khodadadi Karimvand, Somaiyeh; Khorasani, Mojtaba; Safari, Ali Asghar; Vali, Hojatollah [ACS Combinatorial Science, 2020, vol. 22, # 2, p. 70 - 79]

6
[ 98-88-4 ]
[ 110-83-8 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
88%	With aluminum (III) chloride In cyclohexane at -10 - 60℃;	1-7 Example 1 Add 14 ml of cyclohexane and 13.3 g (0.1 mol) of anhydrous aluminum trichloride to the reaction flask.Stir at 0 20 for 0.5 2h,14.1 g (0.1 mol) of benzoyl chloride was added dropwise at -10 to 20 ° C. After the dropwise addition was completed,8.2 g (0.1 mol) of cyclohexene was added dropwise at 20 ° C. After the drop was completed, the reaction was held for 1 to 4 hours.The temperature was then raised to 60 ° C, and the reaction was held for 4-12 hours.The reaction solution after the completion of the incubation reaction was hydrolyzed with a 10% aqueous hydrochloric acid solution, and the aqueous phase was separated.The organic phase was washed and layered twice, and the obtained organic phase was dissolved and dehydrated.16.8 g of a pale yellow solid was obtained with a melting point of 54.0 to 55.0 ° C, a yield of 88.0%, and a purity of 98.5%.
	With aluminium trichloride; cyclohexane at -10 - 45℃;
	With Diethylborane; diethylzinc 1) ether, rt, 3 h; 2) 0 deg C, 3 h; 3) THF, -80 - 0 deg C; 4) THF, -10 deg C, 10 h; Yield given. Multistep reaction;

Reference： [1]Current Patent Assignee: INSIGHT HIGH TECH JIANGSU - CN110294667, 2019, A Location in patent: Paragraph 0019; 0029-0049
[2]Nenitzescu; Gavat [Chemische Berichte, 1937, vol. 70, p. 1883,1885]
[3]Langer, Falk; Schwink, Lothar; Devasagayaraj, Arokiasamy; Chavant, Pierre-Yves; Knochel, Paul [Journal of Organic Chemistry, 1996, vol. 61, # 23, p. 8229 - 8243]

7
[ 2719-27-9 ]
[ 71-43-2 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	at 3℃; for 1h; Heating / reflux;	1.iii; 3; 4 EXAMPLE 1 10.86 g (0.081 mol) of anhydrous aluminum trichloride was added to the cyclohexanecarbonyl chloride solution, and the resulting solution was kept at an internal temperature of below 3° C. with a water/ice bath. After removal of the water/ice bath, the temperature was slowly raised to the reflux temperature and, after one hour, the product was identified as cyclohexyl phenyl ketone with a conversion rate of more than 99% and a selectivity of more than 99% with respect to cyclohexanecarbonyl chloride. [0048] 1H NMR (CDCl3): δ1.22-1.59 (m, 4H), 1.71-1.92 (m, 6H), 3.19-3.32 (m, 1H), 7.41-7.58 (m, 3H), 7.92-7.97 (m, 2H)EXAMPLE 3 [0051] The procedures were performed in the same manner as described in the step (ii) of Example 1, excepting that the ratio of thionyl chloride to cyclohexanecarboxylic acid was varied in the same reaction to prepare cyclohexanecarbonyl chloride. The results are presented in Table 1. [TABLE-US-00001] TABLE 1 Yield of cyclohexanecarbonyl chloride according to change of molar ratio of cyclohexanecarboxylic acid to thionyl chloride Cyclohexanecarboxylic acid:thionyl chloride Conversion (molar ratio) rate Selectivity 1.0:1.0 89 >99 1.0:1.2 96 >99 1.0:1.5 >99 >99 1.0:2.0 >99 >99 [0052] The subsequent Friedel-Crafts reaction was carried out in the same manner as described in Example 1. The obtained product was identified as cyclohexyl phenyl ketone with a conversion rate of more than 99% and a selectivity of more than 99% with respect to cyclohexanecarbonyl chloride.
99%	In hexane at 3℃; for 1.33h; Heating / reflux;	6 EXAMPLE 6 9.36 g (0.070 mol) of anhydrous aluminum trichloride was added to the cyclohexanecarbonyl chloride solution in a water/ice bath with stirring for 20 minutes. After removal of the water/ice bath, the temperature was slowly raised to the reflux temperature and, after one hour, the product was identified as cyclohexyl phenyl ketone with a conversion rate of more than 99% and a selectivity of more than 99% with respect to cyclohexanecarbonyl chloride.
99%	at 3℃; for 1h; Heating / reflux;	5 EXAMPLE 5 The procedures were performed in the same manner as described in the step (iii) of Example 1, excepting that the ratio of anhydrous aluminum trichloride to cyclohexanecarbonyl chloride was varied to prepare cyclohexyl phenyl ketone. The results are presented in Table 2.

88.34%	With 1,1,1,3',3',3'-hexafluoro-propanol at 0℃; for 6h;	1 Example 1: Synthesis of cyclohexyl phenyl ketone. In a 500 ml dry three-necked flask, 73.30 g of cyclohexylcarbonyl chloride (0.50 mol) was added to 117 g of benzene (1.50 mol).And 150 g of hexafluoroisopropanol (0.893 mol), stirred at 0 ° C for 6 h,The reaction is detected by GC or TLC. After the reaction is completed, the solvent is distilled off and further distilled.Cooling gave 83.14 g of a white solid cyclohexyl phenyl ketone, yield 88.34%, GC 96.53%.
84%	With aluminum (III) chloride at 0 - 78℃; for 6h;	1-2 Example 1: In a 500 ml four-necked flask equipped with stirrer, 80.0 g (0.6 mol) of anhydrous AlCl3 was added, and 235 g (3 mol) of benzene was added to the ice water bath such that the temperature was dropped below 0 ° C, and 73.3 g (0.5 mol) prepared cyclohexanoyl chloride (constant pressure funnel) was added dropwise to the bottle, kept at 0-5 ° C during the dropwise addition, and the dropping time was about 30 minutes. After the dropwise addition, the temperature was slowly raised to 78 ° C, and the reaction was refluxed for 6 hours. After completion of the reaction, the reactant was poured into 360 g of 20% dilute hydrochloric acid (1.97 mol) which had been reduced to about 0 ° C, and the mixture was thoroughly stirred, and the phases were separated. The upper organic phase was taken for distillation under reduced pressure to recover benzene, and benzene was distilled off to obtain a pale yellow solid. (A) 85.8 g (content 92%, 0.42 mol), molar yield 84%. The lower acidic layer was distilled under reduced pressure, and 300 g of a hydrochloric acid aqueous solution (B) was distilled off (content: 23%).
74%	at 3℃; for 1h; Heating / reflux;	5 EXAMPLE 5 The procedures were performed in the same manner as described in the step (iii) of Example 1, excepting that the ratio of anhydrous aluminum trichloride to cyclohexanecarbonyl chloride was varied to prepare cyclohexyl phenyl ketone. The results are presented in Table 2.
	With aluminium trichloride
	With aluminium trichloride for 16h; Ambient temperature;
17.2 g	With aluminium trichloride Heating;
	With aluminium trichloride In dichloromethane at 20℃;
	With aluminum (III) chloride at 10 - 60℃; for 1.33333h;	4.a 13.7g of aluminum chloride (103mmoles) were added in portions in 1 hour to a stirred solution of 15g of the cyclohexanecarboxylic acid chloride (lOOmmoles) in 24g of benzene at 10-150C. The mixture was then heated at 6O0C for 20' to complete the reaction. The mixture was cooled to room temperature and poured in 100ml of water. The organic phase was separated and the solved distilled off under vacuum affording 18.6g of an oil.Hl NMR(300MHz, CDCb): δ: 7.90-8.00 (d,2H); 7.40-7.60 (m,3H); 3.20-3.35 (ml H); 1.70- 2.00 (m,5H); 1.20-1 .60 (m,5H).
	With aluminum (III) chloride at 10 - 60℃; for 1.33333h;	4.a a) Acylation Synthesis of cyclohexyl-phenylketone. 13.7 g of aluminum chloride (103 mmoles) were added in portions in 1 hour to a stirred solution of 15 g of the cyclohexanecarboxylic acid chloride (100 mmoles) in 24 g of benzene at 10-15° C. The mixture was then heated at 60° C. for 20' to complete the reaction. The mixture was cooled to room temperature and poured in 100 ml of water. The organic phase was separated and the solved distilled off under vacuum affording 18.6 g of an oil. H1 NMR(300 MHz, CDCl3): δ: 7.90-8.00 (d,2H); 7.40-7.60 (m,3H); 3.20-3.35 (m,1H); 1.70-2.00 (m,5H); 1.20-1.60 (m,5H).
	With aluminum (III) chloride In dichloromethane at 10℃; for 0.583333h; Flow reactor;	13-24 General procedure: (1) Friedel-Crafts reaction section 100: The acyl chloride, aluminum trichloride and the solvent required for Friedel-Crafts reaction are evenly mixed and placed in the first storage tank 1, benzene is placed in the second storage tank 2, and the first feeding pump P1 and The second feeding pump P2 adjusts the feed molar ratio of the flow control reactant, enters the micromixer 3 for mixing, and then enters the first microchannel reactor 4 to perform Friedel-Crafts reaction;(2) Friedel-Crafts reaction intermediate purification section 200: After the material stays in the first microchannel reactor 4 for a certain period of time, it enters the first gas-liquid separation tank 5 to separate hydrogen chloride gas, and absorbs hydrogen chloride tail gas with water to obtain hydrochloric acid; Friedel-Crafts reaction liquid (The first reaction liquid) After accumulating a certain amount in the first gas-liquid separation tank 5, it enters the quenching tank 7. The required hydrochloric acid is placed in the hydrochloric acid storage tank 6, and the metered hydrochloric acid is added by the third feeding pump P3, and under stirring For quenching, the heat generated by the circulating medium in the jacket is taken away, and the temperature of the quenching process is controlled. After the quenching is completed, let it stand for phase separation, take the organic phase GC to detect the conversion rate, and the water phase enters the waste acid tank 8 , The organic phase is in the Friedel-Crafts reaction liquid storage tank 9, and the fourth feeding pump P4 enters the first thin film evaporator 10 to separate the solvent and excess benzene, and the obtained Friedel-Crafts reaction intermediate enters the Friedel-Crafts reaction intermediate storage tank 11 , Excess benzene and recovered solvent enter the recovery solvent and benzene storage tank 12;(3) Chlorination reaction section 300: Friedel-Crafts reaction intermediates are fed into the micromixer 14 from the fifth feeding pump P5 to mix with the chlorine from the chlorine storage tank 13, adjust the chlorine inlet and outlet valves, control the chlorine flow and reaction pressure, and enter the first The chlorination reaction is carried out in the two microchannel reactor 15. The material stays in the second microchannel reactor 15 for a certain period of time and then enters the second gas-liquid separation tank 16 to separate the gas and the second reaction liquid, and sample the GC to detect the conversion rate. Alkaline solution absorbs exhaust gas;(4) Hydrolysis reaction section 400: The sodium hydroxide solution and phase transfer catalyst required for the hydrolysis reaction section are mixed and uniformly placed in the third storage tank 17, fed by the sixth feeding pump P6, and the chlorination reaction intermediate is fed by the seventh The pump P7 feeds materials, enters the micromixer 18 for mixing, and then enters the third microchannel reactor 19 for a certain period of time and then enters the buffer tank 20;(5) Product purification section 500: After a certain amount of material is accumulated in the buffer tank 20, it enters the phase separation tank 21 to stand for phase separation, and the excess sodium hydroxide is neutralized with the hydrochloric acid obtained in step (1), and the water phase enters the waste water tank 22 , The organic phase enters the crude product storage tank 23, the feed pump P8 is added to the second thin film evaporator 24 to distill and purify the finished product into the product storage tank 26, the reboiler enters the reboiler storage tank 25, and the purity of the finished product is detected by GC.

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2004/73068, 2004, A1 Location in patent: Page 3
[2]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2004/73068, 2004, A1 Location in patent: Page 4
[3]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2004/73068, 2004, A1 Location in patent: Page 3-4
[4]Current Patent Assignee: JIAOCHENG COUNTY ZHAOCHEN COAL COKE - CN109534976, 2019, A Location in patent: Paragraph 0015; 0016
[5]Current Patent Assignee: JIANGSU YOUPU BIOCHEMICAL TECH - CN108299172, 2018, A Location in patent: Paragraph 0015; 0016; 0018; 0019
[6]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2004/73068, 2004, A1 Location in patent: Page 3-4
[7]Hey; Musgrave [Journal of the Chemical Society, 1949, p. 3156,3160] Meyer,V.; Scharvin [Chemische Berichte, 1897, vol. 30, p. 1943]
[8]Hartmann; Batzl [European Journal of Medicinal Chemistry, 1992, vol. 27, # 5, p. 537 - 544]
[9]Ho, Bin; Michael Crider; Stables, James P [European Journal of Medicinal Chemistry, 2001, vol. 36, # 3, p. 265 - 286]
[10]Al-Qawasmeh, Raed A.; Lee, Yoon; Cao, Ming-Yu; Gu, Xiaoping; Vassilakos, Aikaterini; Wright, Jim A.; Young, Aiping [Bioorganic and Medicinal Chemistry Letters, 2004, vol. 14, # 2, p. 347 - 350]
[11]Current Patent Assignee: LAMBERTI S.P.A. - WO2009/135895, 2009, A1 Location in patent: Page/Page column 17
[12]Current Patent Assignee: LAMBERTI S.P.A. - US2011/65962, 2011, A1 Location in patent: Page/Page column 5
[13]Current Patent Assignee: CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD. - CN113493372, 2021, A Location in patent: Paragraph 0074-0105

8
[ 712-50-5 ]
[ 37866-45-8 ]
Cyclohexyl-phenyl-methanone O-(2-amino-ethyl)-oxime [ No CAS ]

Reference： [1]Patent: US3937841,1976,A

9
[ 712-50-5 ]
[ 945-49-3 ]

Yield	Reaction Conditions	Operation in experiment
99%	With diethoxymethylane; ferrous acetate In tetrahydrofuran at 65℃; for 24h;
98%	Stage #1: Cyclohexyl phenyl ketone With triethyl borane; sodium methoxide In tetrahydrofuran; diethyl ether at 20℃; for 4h; Inert atmosphere; Stage #2: With sodium hydroxide In tetrahydrofuran; methanol; diethyl ether at 20℃; for 2h;
94%	With C₄₄H₄₀ClN₂NiP₂⁽¹⁺⁾*F₆P^(1-); hydrogen; potassium hydroxide In isopropanol at 120℃; for 12h; Autoclave;	3. Typical procedure for hydrogenation General procedure: Ni-based catalyst (0.01 mmol) was added into a dried autoclave (100 mL). After the addition of fresh distilled iPrOH (20 mL), the autoclave was purged with H2 (30 bar) five times. The mixture was then stirred under 30 bar H2 for 1 h. After releasing the H2 gas in a fumehood, KOH in iPrOH (1 M, 0.2 mL) and ketone (0.5 mmol) were sequentially introduced through an injection port. The autoclave was then pressurized to 40 bar H2 and the reaction mixture stirred at 120 °C for 12 h. After cooling down to room temperature and subsequently releasing the H2 pressure in a fumehood, the mixture was concentrated and purified by chromatograph on a silica-gel column. The conversion of the product was determined by GC.

93%	Stage #1: Cyclohexyl phenyl ketone With sodium tetrahydridoborate In ethanol at 20℃; Cooling with ice; Stage #2: With hydrogenchloride In ethanol; water monomer
91.2%	With hydrogen In methanol at 90℃; for 9h; Autoclave;	2.1 1) 1000ml high-pressure dad, add 700ml of methanol as a solvent, then add 188g cyclohexyl phenyl ketone, 18g hydrogenation catalyst nickel catalyst AMG-1200; was added, sealed reactor, nitrogen replaced the kettle air, pass Into H2 to pressure 4.OMPa, open stirring, heating to 90 °C for the reaction, the reaction 9 hours, the point of detection plate cyclohexyl phenyl ketone disappeared into cyclohexyl (phenyl) methanol; reaction was stopped, cooled, Filtered and concentrated to give crude cyclohexyl (phenyl) methanol, and then purified by column to give 173.3g of pure cyclohexyl (phenyl) methanol, the yield was 91.2%
89%	With N,N,N,N,-tetramethylethylenediamine; diethoxymethylane at 65℃; for 24h;
89%	With tripotassium phosphate tribasic; 1-(4-(dimethylamino)phenyl)ethyl alcohol In 1,4-dioxane at 120℃; for 16h; Inert atmosphere; Sealed tube;
87%	With sodium tetrahydridoborate In methanol at 20℃; for 2h;
75%	With CdS(x)Se(1-x) x:0-1;; caesium acetate; para-thiocresol In toluene for 15h; Sealed tube; Inert atmosphere; Irradiation;
73%	With sodium tetrahydridoborate In methanol for 0.166667h;
62%	With methanol; sodium tetrahydridoborate at 0℃; for 0.0833333h;	Typical procedure for reduction of ketones General procedure: To a mixture of methanol (10 mL), a ketone (1 mmol),and 50 mg of freshly prepared CAC[4]-SG (containing0.005 mmol CSC[4]A) at 0 °C, was slowly added 200 mgNaBH4.The reaction mixture was stirred until TLC showedthe ketone is consumed. At this point, the reaction mixturewas vacuum filtered using a sintered glass funnel and the filtrate was quenched with diionized water and extracted with ethyl acetate. The organic layer was dried over sodiumsulfate and the volatiles were evaporated at reduced pressureto obtain the corresponding alcohol. In all cases, productswere characterized by comparison of their spectroscopicdata (IR and 1H-NMR spectra) and melting points withthose of authentic samples. The solid catalyst which wasseparated from the reaction mixture by filtration was thenwashed consecutively with dichloromethane, diethyl ether,methanol, and hexane and dried for 12 h at 150 °C. The recycledcatalyst was reused in next reactions without loosing itsactivity. Elemental analysis showed no significant changes inchemical composition of the catalyst after recovery.
43%	With potassium-t-butoxide; 1-hydrosilatrane In tetrahydrofuran; N,N-dimethyl-formamide for 0.5h; Inert atmosphere;	5. General procedure for the racemic reduction of ketones General procedure: To a 25 mL round-bottomed flask containing 5 mL N,N-dimethylformamide, were added 1-hydrosilatrane(0.263 g, 2.0 mmol), and ketone (1.0 mmol). The resulting solution was stirred for 1 minute, after which 1M tBuOK in THF (1.0 mmol, 1.0 mL) was added. Reaction mixture was allowed to stir for 30 min. Reaction was quenched with 25 mL 3M HCl, and extracted with 30 mL ethyl acetate. Organic layer was washed with brine (50 mL x 3), and dried with anhydrous sodium sulphate. After filtration, the solvent was removed under vacuum to yield product. No further steps were taken for purification.
	With 1,2-bis(3,5-di-t-butylsalicyl)benzene; tris(methyl)aluminum; diisobutylaluminium hydride In diethyl ether; dichloromethane at -78℃; for 1h; relative reactivity (vs acetophenone), further ligands;
	With potassium hydroxide In isopropanol at 130℃;
	With sodium tetrahydridoborate In ethanol
	With hydrogen
	With sodium tetrahydridoborate In methanol for 3h; Ambient temperature;
	With Zr-100 Al-free Zr-zeolite beta; isopropanol for 24h;
	With 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole; 1,6-bis-(dimethylamino)pyrene; water monomer In N,N-dimethyl-formamide Irradiation;
95 % Chromat.	With potassium hydroxide; isopropanol at 82℃; for 24h;
	With sodium tetrahydridoborate
	With sodium tetrahydridoborate
	Multi-step reaction with 2 steps 1: Rh catalyst / benzene 2: NaOMe / methanol
	Multi-step reaction with 2 steps 1: Rh catalyst / benzene 2: NaOMe / methanol
	With isopropanol at 30℃; for 24h; Microbiological reaction;
	With sodium tetrahydridoborate In methanol at 0℃; Inert atmosphere;
	With [1-(2-aminomethylphenyl)-3-methylimidazol-2-ylidene]-(η5-pentamethylcyclopentadienyl)(pyridine)ruthenium(II) hexafluorophosphate; potassium-t-butoxide; hydrogen at 25℃; for 2h;
	With sodium tetrahydridoborate In methanol Inert atmosphere;
	With methanol; borane-ammonia complex at 20℃; Inert atmosphere;	5.4. Reactions of ketones and aldehydes with AB in methanol General procedure: A 0.5 mm NMR tube was charged with ketone or aldehyde (0.2 mmol), AB (0.1 mmol), and deuterated methanol. The tube was covered with a plastic cap and inserted into the NMR machine after shaking. The reaction courses were monitored by 1H and 11B NMR every several minutes (depending on the reaction rates). The typical resonances of the starting materials gradually decreased while new signals of the saturated products appeared. After the ketone or aldehyde disappeared completely in the 1H NMR spectrum, 13C NMR spectrum was recorded. For a large scale reaction in normal methanol, the solvent and all volatile compounds (trimethyl borate and ammonia) were removed by high vacuum after the reaction, and the remaining alcohol was pure to the limit of the NMR with nearly 100% yield.
	With sodium tetrahydridoborate
	With sodium tetrahydridoborate In methanol
	With sodium tetrahydridoborate In ethanol Inert atmosphere;
	With sodium tetrahydridoborate; ethanol at 0 - 20℃;	199 Cyclohexyl phenyl ketone (5.0 g, 27 mmol) was dissolved in ethanol (50 mL) and cooled by ice. Sodium borohydride (510 mg, 13.5 mmol) was added thereto at 0° C. The completion of the addition, the mixture was heated to a room temperature, and the disappearance of the raw material was confirmed by TLC. The reaction solution was concentrated and then diluted with water, and the diluted solution was neutralized with a 1-N hydrochloric acid aqueous solution. Ethyl acetate was added thereto, the mixture was subjected to extraction. Then the extract was dried over sodium sulfate. The solvent was distilled off, and the residue was used for the next step without purification. The resulting viscous oil was dissolved in dichloromethane (10 mL), and thionyl chloride (10 mL, 140 mmol) was added dropwise thereto at a room temperature. After the dropping was completed, the completion of the reaction was confirmed by TLC. After the completion of the reaction, toluene was added to the reaction mixture, and unreacted thionyl chloride was distilled off. The resulting light-yellow oil and 1-carboethoxy-4-hydroxypiperidine (2.1 g, 12 mmol) were mixed, and the mixture was stirred at an oil bath temperature of 130° C. overnight. After the completion of the reaction was confirmed by TLC, the reaction mixture was allowed to cool down. Ethyl acetate was added to the resulting residue, and then the resulting mixture was washed with water. The organic layer was dried over sodium sulfate, and then the solvent was distilled off. Thus a brown oil was obtained. The resulting oil was purified by silica gel column chromatography (hexane/ethyl acetate (volume ratio)=10:1) to give the title compound (5.1 g, 510). 1H-NMR (CDCl3, δ): 0.8-1.4 (3H,m), 1.4-2.2 (14H,m), 3.0-3.3 (3H,m), 3.3-3.4 (1H,m), 3.5-3.8 (2H,m), 3.99 (1H,d,J=8 Hz), 4.10 (2H,q,J=7.0 Hz), 7.1-7.4 (5H,m). MS (m/z): 345 (M+).
	With sodium tetrahydridoborate In ethanol Inert atmosphere;
	Stage #1: Cyclohexyl phenyl ketone With C₃₃H₅₈FeN₃PSi₂; phenylsilane In toluene at 20℃; for 4h; Inert atmosphere; Glovebox; Green chemistry; Stage #2: With sodium hydroxide In toluene for 1h; Green chemistry;
	With sodium tetrahydridoborate In ethanol at 0 - 20℃;
	With sodium tetrahydridoborate In ethanol at 0 - 20℃;
	With RuCl(4-phenyl-2-aminomethylbenzo[h]quinoline-H)(1,1′-bis(diphenylphosphino)ferrocene); sodium isopropanolate In propan-1-ol at 82℃; for 0.666667h; Inert atmosphere;
	Stage #1: Cyclohexyl phenyl ketone With cyclopentadienyl iron(II) dicarbonyl dimer; diethoxymethylane at 100℃; for 48h; Stage #2: With water monomer; sodium hydroxide In methanol
	With sodium tetrahydridoborate In methanol; isopropanol at 0 - 20℃; Inert atmosphere;
	With C₅₄H₄₃ClFeN₂P₂Ru; sodium isopropanolate; isopropanol In neat (no solvent) at 82℃; for 0.666667h; Inert atmosphere;	23 Example 23 Transfer hydrogenation of ketones. The catalyst (2.5 μηιοΙ) used was dissolved in 2.5 mL of 2-propanol. The ketone (2.0 mmol) was dissolved in 2-propanol and the solution (final volume 19.4 mL) was heated under argon at reflux. By addition of 400 μ of NaO/'Pr (0.1 M, 40 μηιοΙ) in 2-propanol and 200 of the solution containing the catalyst the reduction of the ketone started immediately and the yield was determined by GC after reaction times given in the Table 1 Table 1. Catalytic transfer hydrogenation of ketones (0.1 M) with complexes 13-20 (S/C = 5000- 20000) and NaO/'Pr (2 mol %) in 2-propanol at 82 °C. Conv. Entry Complex Ketone S (M) S/C t (min) (%)a 1 13 23 0.1 10000 2 98 2 14 23 0.1 5000 10 99 3 14 23 0.1 10000 15 99 4 14 23 0.1 20000 15 98 5 14 23 0.2 10000 15 96 6 14 23 0.5 10000 15 93 7 15 23 0.1 10000 2 97 8 15 23 0.1 20000 10 97 9 16 23 0.1 10000 10 96 10 17 23 0.1 10000 10 95 1 1 18 23 0.1 10000 20 93 12 19 23 0.1 10000 10 97 13 20 23 0.1 10000 2 97b 14 17 24 0.1 10000 10 94 15 15 25 0.1 10000 20 99 16 15 26 0.1 10000 40 95 17 18 26 0.1 10000 20 93 18 13 27 0.1 5000 40 99 19 18 27 0.1 5000 14 h 97 20 13 28 0.1 5000 40 99 21 18 28 0.1 5000 14 h 98 22 15 29 0.1 10000 10 99 23 15 30 0.1 10000 10 98 24 17 31 0.1 10000 5 99 25 17 32 0.1 10000 5 99 a The conversion was determined by GC analysis. b ee = 85% (S) The catalysts of this investigation reduce a wide structural variety of ketones. In 2-propanol at reflux and in the presence of NaO/'Pr (2 mol %) the ketones in Table 1 are efficiently reduced via transfer hydrogenation with a S/C ratio up to 20000/1 . The ketones are selected to cover a broad range of structures: alkyl-arylketones 23-27, benzophenone 29 and dialkylketones 28, 30-32. Ketones 27 and 28 having bulky tertBu substituents are reduced with near complete conversion of the substrate. Reduction of C=0 bond of 5-hexen-2-one 30 is entirely chemoselective, without saturation or isomerization of the terminal C=C bond. The use of methyl-benzo[ ?]quinoline or phenyl-benzo[ ?] quinoline ligands allows a fine tuning of catalyst activity and selectivity. The chiral complex 20 containing the (S,R)-JOSIPHOS ligand reduced 23 quantitatively to (S)-1 -phenylethanol in 2 min and with 85 % ee.
	With sodium tetrahydridoborate
	With C₁₉H₃₃ClIrN₃O; sodium isopropanolate In isopropanol for 1h; Inert atmosphere; Reflux;
	With sodium tetrahydridoborate In methanol at 20℃;
99 %Chromat.	With C₁₈H₂₁BrMnN₃O₃; potassium-t-butoxide; isopropanol at 40℃; for 24h;
	With [Ni₂((R)-1-phenyl-N-(pyridine-2-ylmethylene)ethanamine)₄-μ-Br₂][NiBr₄]; potassium-t-butoxide; isopropanol at 82℃; for 24h; Inert atmosphere; Schlenk technique;
1.01 g	With sodium tetrahydridoborate In ethanol at 20℃;	Cyclohexyl(phenyl)methanol Sodium borohydride (0.201 g, 5.31 mmol) was added to a solution of cyclohexyl (phenyl)methanone (1 g, 5.31 mmol) in ethanol (20 mL) and the mixture was stirred at room temperature overnight. The reaction mixture was evaporated under vacuum. The residue was dissolved in DCM and washed sequentially with water and brine. The organic layer was then dried over MgSO4, filtered and evaporated under reduced pressure to give the product as a colorless oil (1.01 g). LCMS. [Injection Vol = 3 mL, Start %B = 2, Final %B =98, Gradient Time = 1.5 min, Flow Rate = 0.8 mL / min, Wavelength = 220 nm, Solvent Pair= Water/Acetonitrile/TFA, Solvent A = 100% Water/ 0.05% TFA, Solvent B = 100% Acetonitrile/0.05% TFA, Column = Waters Aquity BEH C182.1 X 50 mm 1.7U MW1, Oven Temp = 40] RT = 1.255 min. Mass not observed as MWt < 200. 1H NMR (400 MHz, DMSO-d6) d 7.34-7.17 (m, 5H), 5.01 (d, J=4.4 Hz, 1H), 4.23 (dd, J=6.4, 4.6 Hz, 1H), 1.89-0.85 (m, 11H).
	With sodium tetrahydridoborate In methanol
	With sodium tetrahydridoborate In tetrahydrofuran; methanol at 0 - 20℃; for 3h;

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10
[ 712-50-5 ]
(S)-cyclohexylphenylmethanol [ No CAS ]
(R)-cyclohexylphenylmethanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With (mer-[(S,S)-1,5-dimethyl-2,4-bis(4-phenyl-1,3-oxazolin-2-yl)benzene^(1-)]Ru(CO)Cl)2(ZnCl₂); hydrogen; sodium methylate; (-)-(S)-1-Anthracen-9-ylethanol In isopropyl alcohol at 40℃; for 42h; Inert atmosphere; Autoclave; optical yield given as %ee; enantioselective reaction;
	With lithium aluminium tetrahydride; 3-O-cyclohexylmethyl-1,2-O-cyclohexylidene-α-D-glucofuranose In diethyl ether for 2.5h; Heating; LiAlH4 concentration effect on enantiomeric excess; reaction in presence of various amounts of EtOH; asymmetric reduction of ketones and isoelectronic ketone oximes with LiAlH4-3-O-cyclohexylmethyl-1,2-O-cyclohexylidene-α-D-glucofuranose complex;
	With n-butyllithium; chiral titanocene 1,1'-binaphth-2,2'-diolate; phenylsilane; tetrabutyl ammonium fluoride 1.) benzene, hexane, 2.5 d, 2.) benzene, hexane, THF; Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts;

	With 8-binap)(cod)>BF4; hydrogen; 2-[(2-dimethylaminophenyl)(phenyl)phosphine]-N,N-dimethylaniline In 1,4-dioxane; methanol at 90℃; for 166h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
	With potassium <i>tert</i>-butylate; hydrogen In isopropyl alcohol at 24 - 30℃; for 48h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
	With Rhizopus arrhizus In ethanol for 168h; Title compound not separated from byproducts;
	With (R)-3,5-xyl-MeO-BIPHEP; copper(l) chloride In toluene at -50℃; for 10h; Title compound not separated from byproducts;
	With polymethylhydrosiloxane; copper(l) chloride; sodium t-butanolate In toluene at -78 - 20℃; for 1h; Title compound not separated from byproducts;
	With C₄₉H₄₇O₂N₂⁽¹⁺⁾*BF₄^(1-); diphenylsilane; silver trifluoromethanesulfonate In tetrahydrofuran at 0℃; for 30h; Title compound not separated from byproducts;
	With carbonylhydridotris(triphenylphosphine)iridium(I); N,N'-bis[o-(diphenylphosphino)benzylidene]-1R,2R-diaminocyclohexane In isopropyl alcohol at 75℃; for 3h; Title compound not separated from byproducts;
	With formic acid; (R,R)-1,2-diphenylethylenediamino ruthenium derivative; triethylamine at 40℃; for 24h; Title compound not separated from byproducts;
	With sodium tetrahydroborate; ethanol; chloroform In tetrahydrofuran at -20℃; for 15h; Title compound not separated from byproducts;
	With formic acid; triethylamine at 40℃; for 24h; Title compound not separated from byproducts;
	With 2-hydroxytetrahydrofuran; sodium tetrahydroborate; ethanol In chloroform at -20℃; for 12h;
	With NaY zeolite; (+) norephedrine In hexane Irradiation; Title compound not separated from byproducts.;
	With NaY zeolite; (1R,2S)-norephedrine In hexane Irradiation; Title compound not separated from byproducts.;
	With dimethylsulfide borane complex In tetrahydrofuran at 20℃; Title compound not separated from byproducts.;
		4 Table 5a lists the results from the enantioselective reduction of various representative aromatic and alkyl ketones with 10% spiroborates esters 6 and 10 as catalyst. TABLE 5a Entry Substrate Cat. Yield % ee % 1 4-phenylbutan-2-one 10 90 72 2 1-indanone 6 94 97 3 1-indanone 10 96 96 4 1-tetralone 10 99 100 5 cyclohexyl phenyl ketone 10 83 60 6 p-chloroacetophenone 10 98 99 7 3-chloropropiophenone 10 86 94 8 2-chloro-2',4'-difluoroacetophenone 10 88 98 9 2,2,2-trifluoro-acetophenone 10 97 82 10 1-adamantyl methyl ketone 10 98 99 The first column lists the entry or reaction number. The second column identifies the ketone. The third column identifies the catalyst. The fourth column lists the yield. The last column lists the enatioselectivity. For entry 6, this was determined by GC on a chiral column (CP-Chiralsil-DexCB). For entries 1-4 and 8-10, this was determined by 31P-NMR of derivative with a phosphonate (CDA).
	With bis(1,5-cyclooctadiene)diiridium(I) dichloride; potassium <i>tert</i>-butylate; isopropyl alcohol; N,N'-bis-[(S)-1'-phenylethyl]-(1R,2R,4R,5R)-1,2-diamino-4,5-dimethyl-cyclohexane at 55℃; for 21h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
	With trans-(R, R)-[Fe(Ph₂PCH₂CH=NCH(Ph)CH(Ph)N=CHCH₂PPh₂)(CH₃CN)(CO)][BPh₄]2; potassium <i>tert</i>-butylate In isopropyl alcohol at 22℃; for 1.41667h; Inert atmosphere; optical yield given as %ee;
	Stage #1: Cyclohexyl phenyl ketone With diphenylsilane; diethylzinc; (2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-(2,3:12,13:22,23)-tributano-(6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,13H,14H,15H,20H,21H,22H,23H,24H,25H,30H)-octadecahydro-⁽³⁰⁾-annulene In hexane; toluene at 20℃; for 24h; Inert atmosphere; Stage #2: With sodium hydroxide In methanol; hexane; toluene at 20℃; for 1h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
	With dimethylsulfide borane complex; (S)-1-methyl-3,3-diphenyl-hexahydropyrrolo[1,2-c][1,3,2]oxazaborole In tetrahydrofuran at 30℃; for 15h; optical yield given as %ee; enantioselective reaction;
	With copper (II)-fluoride; phenylsilane; (S)-2,2',6,6'-tetramethoxy-4,4'-bis(di(3,5-xylyl)phosphino)-3,3'-bipyridine In toluene at -10℃; for 24h; optical yield given as %ee; enantioselective reaction;
	With iridium(III) chloride hydrate; C₂₄H₂₈N₂O₂S; hydrogen; sodium hydroxide In methanol at 40℃; for 24h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
	With (SRu)-carbonylchloro-η5-[1-(2-((S)-4-isobutyloxazolinylphenyl))-2,3,4,5-tetraphenylcyclopentadienyl]ruthenium(II); isopropyl alcohol; potassium hydroxide at 82℃; for 3h; Inert atmosphere; optical yield given as %ee;
	With (R)-C₄-TunePhos; palladium(II) trifluoroacetate; hydrogen; salicylic acid In 2,2,2-trifluoroethanol at 20℃; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	The Typical Procedure for Asymmetric Hydrogenation (R)-C4-Tunephos (3.6 mg, 0.006 mmol) and Pd(CF3CO2)2 (1.7 mg, 0.005 mmol) were placed in a dried Schlenk tube under nitrogen atmosphere, and degassed anhydrous acetone was added. The mixture was stirred at room temperature for 1 h. The solvent was removed under vacuum to give the catalyst. To this was added dry TFE (2 mL) followed by ketone and additive under a hydrogen atmosphere. Then the mixture was stirred at room temperature. After confirmation of consumption of substrate by TLC, GC or 1H NMR, and then the hydrogen gas was slowly released. The conversion was directly determined by 1H NMR spectroscopy or GC. The enantiomeric excess was determined by HPLC after purification on silica gel using petroleum ether and EtOAc or directly determined by GC.
	With C₂₈H₃₄N₂Rh⁽¹⁺⁾*F₆P^(1-); potassium <i>tert</i>-butylate; isopropyl alcohol at 20℃; for 1.5h; Inert atmosphere; enantioselective reaction;
	With (2S)-N-{(1R,2R)-2-[(S)-pyrrolidine-2-carboxamido]-1,2-diphenylethyl}pyrrolidine-2-carboxamide; [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; sodium formate In water at 60℃; for 24h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
	Stage #1: Cyclohexyl phenyl ketone With silver tetrafluoroborate; diethoxymethylane; C₂₉H₃₇ClIrN₃O₂ In 2-methyltetrahydrofuran at 20℃; for 20h; Stage #2: With methanol; potassium carbonate In 2-methyltetrahydrofuran at 20℃; for 2h; optical yield given as %ee; enantioselective reaction;
	With bis(triphenylphosphine)carbonyliridium(I) chloride; (R)-N,N'-bis[2-(piperidin-1-yl)benzylidene]propane-1,2-diamine; potassium hydroxide In isopropyl alcohol at 75℃; for 10h; optical yield given as %ee; enantioselective reaction;
	With diethyl zinc; diphenylsilane; (2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-(2,3:12,13:22,23)-tributano-(6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,13H,14H,15H,20H,21H,22H,23H,24H,25H,30H)-octadecahydro-⁽³⁰⁾-annulene In hexane; toluene at 20℃; for 24h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
79 % ee	With carbonylhydridotris(triphenylphosphine)iridium(I); C₃₂H₄₃N₄P; isopropyl alcohol; potassium hydroxide at 40℃; for 5h; Schlenk technique; Inert atmosphere; enantioselective reaction;	ATH of aromatic ketones General procedure: To a 50mL Schlenk tube were added Ir complex (0.005mmol) and ligand 5 (0.005mmol). Under nitrogen atmosphere, freshly distilled and degassed iPrOH (10mL) were introduced. After stirring at 40°C for 30min, an appropriate amount of KOH/iPrOH solution was then added. The mixture was continually stirred for another 15min, ketone was then introduced and the mixture was stirred at 40°C for a certain period of time. At the end of experiment, the reaction products were analyzed by GC using a chiral CP-Chiralsil-Dex CB column.
13 % ee	With (S)-3-hexadecyl-1-(1-hydroxypropan-2-yl)-1H-imidazol-3-ium bromide; triethylamine In para-xylene; water Irradiation; Photolysis; Inert atmosphere; stereoselective reaction;
	With chloro(1,5-cyclooctadiene)rhodium(I) dimer; potassium <i>tert</i>-butylate; hydrogen; (1R,2R)-N-(2-diphenylphosphanylbenzyl)cyclohexane-1,2-diamine In isopropyl alcohol; <i>tert</i>-butyl alcohol at 50℃; for 1h; Schlenk technique; Optical yield = 72 %ee;
89 % ee	With Ir⁽¹⁺⁾C₈H₁₂C₂₅H₂₈N₂P^(1-); potassium <i>tert</i>-butylate; hydrogen; isopropyl alcohol In <i>tert</i>-butyl alcohol at 50℃; for 16h; Autoclave; Schlenk technique; enantioselective reaction;
37 % ee	Stage #1: Cyclohexyl phenyl ketone With lithium aluminium tetrahydride; C₃₇H₄₅BrFeNO₂P₂⁽³⁺⁾*BF₄^(1-); hydrogen In tetrahydrofuran at 50℃; for 0.0833333h; Stage #2: In tetrahydrofuran; tert-Amyl alcohol for 0.166667h; Stage #3: With potassium <i>tert</i>-butylate In tetrahydrofuran Inert atmosphere; Glovebox; enantioselective reaction;
> 98 %Spectr.	With C₄₇H₄₀O₄P₂Rh⁽¹⁺⁾*CF₃O₃S^(1-); diphenylsilane; hydrogen In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Autoclave; enantioselective reaction;
79 % ee	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; C₂₉H₃₆N₂O₈S; sodium isopropylate; lithium chloride In tetrahydrofuran; isopropyl alcohol at 20℃; for 3h; Inert atmosphere; Schlenk technique; Overall yield = 14 %; Overall yield = 27 mg; enantioselective reaction;
70 % ee	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; C₃₁H₄₀N₂O₈S; sodium isopropylate; lithium chloride In tetrahydrofuran; isopropyl alcohol at 20℃; for 3h; Inert atmosphere; Schlenk technique; Overall yield = 12 %; enantioselective reaction;
84.9 % ee	With C₄₄H₅₂FeN₄P₂⁽²⁺⁾*2BF₄^(1-); sodium t-butanolate In isopropyl alcohol at 75℃; for 15h; Glovebox; Schlenk technique; Inert atmosphere; Overall yield = 97 %; Overall yield = 27.9 %Chromat.; enantioselective reaction;
86.2 % ee	With C₅₀H₆₈FeN₄P₂⁽²⁺⁾*2BF₄^(1-); sodium t-butanolate In isopropyl alcohol at 75℃; for 5h; Glovebox; Schlenk technique; Overall yield = 78.7 %; enantioselective reaction;
89 % ee	Stage #1: Cyclohexyl phenyl ketone With silver tetrafluoroborate; diethoxymethylane; C₃₀H₃₉ClIrN₃O₂ In tetrahydrofuran at 20℃; for 15h; Stage #2: With potassium carbonate In tetrahydrofuran; methanol at 20℃; for 2h; Overall yield = 57 %; enantioselective reaction;
	With diphenylsilane; diethylzinc In toluene at 20℃; for 24h; Optical yield = 84 %ee; enantioselective reaction;
62 % ee	With phenylsilane; C₄₂H₃₀BF₅S In neat (no solvent) at 20℃; for 96h; Inert atmosphere; Glovebox; Overall yield = 24 %; Overall yield = 5.3 mg; enantioselective reaction;
74 % ee	With (R)-bis[[N-2-diphenylphosphinite-2-phenyl]-1,1'-ferrocenylmethyldiamine(dichloro η⁵-pentamethylcyclopentadienyl iridium(III))]; isopropyl alcohol; potassium hydroxide at 82℃; for 7h;
71 % ee	With (2R)-2-(ferrocenylmethylamino)-2-phenylethyldiphenylphosphinito(dichloro(ɳ⁵-pentamethylcyclopentadienyl)iridium(III)); isopropyl alcohol; potassium hydroxide at 82℃; for 4h; Inert atmosphere; Schlenk technique; enantioselective reaction;	General procedure for the transfer hydrogenation of ketones General procedure: Typical procedure for the catalytic hydrogen transfer reaction: a solution of iridium complexes 17-24 (0.005 mmol), KOH (0.025 mmol) and the corresponding ketone (0.5 mmol) in degassed 2-propanol (5 mL) was refluxed until the reaction completed. Then, a sample of the reaction mixture is taken off, diluted with acetone and analyzed immediately by GC, conversions obtained are related to the residual unreacted ketone.
78 % ee	With (2S)-2-(ferrocenylmethylamino)-2-phenylethyldiphenylphosphinito(dichloro(ɳ⁵-pentamethylcyclopentadienyl)iridium(III)); isopropyl alcohol; potassium hydroxide at 82℃; for 4h; Inert atmosphere; Schlenk technique; enantioselective reaction;	General procedure for the transfer hydrogenation of ketones General procedure: Typical procedure for the catalytic hydrogen transfer reaction: a solution of iridium complexes 17-24 (0.005 mmol), KOH (0.025 mmol) and the corresponding ketone (0.5 mmol) in degassed 2-propanol (5 mL) was refluxed until the reaction completed. Then, a sample of the reaction mixture is taken off, diluted with acetone and analyzed immediately by GC, conversions obtained are related to the residual unreacted ketone.
1 % ee	With (S,S)-trans-[FeCl(CO)-(PPh₂CH₂CH₂NHCHPhCHPhNCHCH₂PPh₂)]BPh₄; tetrabutylammonium tetrafluoroborate; water; potassium formate In 2-methyltetrahydrofuran at 65℃; for 1.5h; Inert atmosphere; Schlenk technique; enantioselective reaction;
50% ee	With (S)-bis[[N-(2-diphenylphosphinite-1-benzyl)ethyl]-1,1'-ferrocenylmethyldiamine(dichloro η⁶-p-cymene ruthenium(II))]; isopropyl alcohol; potassium hydroxide at 82℃; for 8h; Inert atmosphere; Schlenk technique; enantioselective reaction;	General procedure for the transfer hydrogenation of ketones General procedure: The standard procedure for the catalytic hydrogen-transfer reaction was as follows. A solution of the corresponding ferrocenyl phosphinite complexes 1-15 (0.01 mmol), KOH (0.05 mmol) and the methyl alkyl ketones or alkyl/arylketones (1 mmol) in isopropanol (10 mL) was refluxed until completion of the reaction. A sample of the reaction mixture was taken, diluted with acetone and analyzed immediately by GC. Conversions obtained are related tothe residual unreacted methyl/alkyl ketones or alkyl/arylketones.
56 % ee	With (S)-bis[[N-(2-diphenylphosphinite-1-phenyl)ethyl]-1,1'-ferrocenylmethyldiamine(dichloro η⁶-p-cymene ruthenium(II))]; isopropyl alcohol; potassium hydroxide at 82℃; for 8h; Inert atmosphere; Schlenk technique; enantioselective reaction;	General procedure for the transfer hydrogenation of ketones General procedure: The standard procedure for the catalytic hydrogen-transfer reaction was as follows. A solution of the corresponding ferrocenyl phosphinite complexes 1-15 (0.01 mmol), KOH (0.05 mmol) and the methyl alkyl ketones or alkyl/arylketones (1 mmol) in isopropanol (10 mL) was refluxed until completion of the reaction. A sample of the reaction mixture was taken, diluted with acetone and analyzed immediately by GC. Conversions obtained are related tothe residual unreacted methyl/alkyl ketones or alkyl/arylketones.
62 % ee	With C₃₅H₄₂ClFeNOP₂; potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran at 50℃; for 1.5h; Autoclave; enantioselective reaction;
	With [(3S)-6-methyl-7-phenyl-3-isopropyl-2,3-dihydroimidazo[5,1-b]oxazol-5-ylidene](1,5-cyclooctadiene)iridium chloride; potassium <i>tert</i>-butylate In isopropyl alcohol at 75℃; for 3h; Inert atmosphere; Overall yield = 38 %; Optical yield = 20 %ee; enantioselective reaction;
80 % ee	With lithium aluminium tetrahydride; tert-Amyl alcohol; trans-(S,S)-[Fe(Ph₂PCH(Ph)CH(Me)NCHCH₂PCy₂)(C₀)2(Br)][BF₄]; potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran at 50℃; for 12h;
68 % ee	With (2R)-2-[benzyl([6-({benzyl[(1R)-2-[(diphenylphosphanyl)oxy]-1-phenylethyl]amino}methyl)pyridin-2-yl]methyl})amino]-2-phenylethyl diphenylphosphinite bis(dichloro-η⁶-p-cymeneruthenium(II)); isopropyl alcohol; potassium hydroxide at 82℃; for 4h; Inert atmosphere; Schlenk technique; enantioselective reaction;	2.3. General procedure for the asymmetric transfer hydrogenation of ketones General procedure: Typical procedure for the catalytic hydrogen-transfer reaction: a solution of the Ru(II)-complexes 17-24 (0.005 mmol), KOH (0.025mmol) and the corresponding ketone (0.5 mmol) in degassed 2-propanol (5 mL) was refluxed until the reaction was completed. Periodically samples taken from the reaction medium were passed through acetone silica gel column and conversion rates were observed in gas chromatography, which were calculated based on unreacted ketone.
76 % ee	With (2S)-1-[(2S)-2-[(diphenylphosphanyl)oxy]propyl][(1R)-1-phenylethyl]amino}pro-pan-2-yldiphenylphosphinitobis[dichloro(η⁶-benzene)ruthenium(II)]; isopropyl alcohol; potassium hydroxide at 82℃; for 2h; Schlenk technique; Inert atmosphere; enantioselective reaction;	4.3 General procedure for the transfer hydrogenation of ketones General procedure: Typical procedure for the catalytic hydrogen-transfer reaction: a solution of the ruthenium complexes 5-8 (0.005mmol), KOH (0.025mmol) and the corresponding ketone (0.5mmol) in degassed isoPrOH (5mL) was refluxed until the reaction was completed. After this time, a sample of the reaction mixture was taken off, diluted with acetone and analyzed immediately by GC, conversions obtained are related to the residual unreacted ketone. Furthermore, 1H NMR spectral data for the resultant products were consistent with previously reported results
53 % ee	With C₄₃H₄₀BrFeN₂OP₂⁽¹⁺⁾*C₂₄H₂₀B^(1-); potassium <i>tert</i>-butylate; isopropyl alcohol at 28℃; for 1h; enantioselective reaction;
2 % ee	With C₃₄H₄₀ClIrN₃⁽¹⁺⁾*F₆P^(1-); potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran at 50℃; for 2h; Inert atmosphere;
10 % ee	With hydrido(η²,η²-cycloocta-1,5-diene)[o-metalated-3-((1S,2S)-1,2-diphenyl-2-aminoethyl)-1-mesityl-butylimidazol-2-ylidene]iridium hexafluorophosphate; potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran at 50℃; for 2h; Inert atmosphere;
60 % ee	With (1R)-2-{benzyl[(1S)-1-(naphthalen-1-yl)ethyl]amino}-1-phenylethyldiphenylphosphite; isopropyl alcohol; potassium hydroxide at 82℃; for 4h; Schlenk technique; Inert atmosphere; enantioselective reaction;	4.1. General procedure for the transfer hydrogenation of ketones General procedure: Typical procedure for the catalytic hydrogen-transfer reaction: asolution of the ruthenium complexes (5-8) (0.005 mmol), KOH(0.025 mmol) and the corresponding ketone (0.5 mmol) indegassed isoPrOH (5 mL)was refluxed until the reaction completed.A sample of the reaction mixture was taken off, diluted withacetone and analyzed immediately by GC, the conversions obtainedare related to the residual unreacted ketone. Furthermore, 1H NMRspectral data for the resultant products were consistent with previouslyreported results.
78 % ee	With (1R)-2-{benzyl[(1S)-1-(naphthalen-1-yl)ethyl]amino}-1-phenylethyldiphenyl phosphinito[dichloro(η⁶-benzene)ruthenium(II)]; isopropyl alcohol; potassium hydroxide at 82℃; for 2h; Schlenk technique; Inert atmosphere; enantioselective reaction;	4.1. General procedure for the transfer hydrogenation of ketones General procedure: Typical procedure for the catalytic hydrogen-transfer reaction: asolution of the ruthenium complexes (5-8) (0.005 mmol), KOH(0.025 mmol) and the corresponding ketone (0.5 mmol) indegassed isoPrOH (5 mL)was refluxed until the reaction completed.A sample of the reaction mixture was taken off, diluted withacetone and analyzed immediately by GC, the conversions obtainedare related to the residual unreacted ketone. Furthermore, 1H NMRspectral data for the resultant products were consistent with previouslyreported results.
8 % ee	With (1S,2R)-2-Amino-1,2-diphenylethanol; sodium hydride; 1-hydrosilatrane In tetrahydrofuran; mineral oil at -30℃; for 6h; Inert atmosphere; enantioselective reaction;	2. General procedure for the asymmetric reduction of ketones General procedure: To a flame dried 8 mL screw cap vial, under argon, were added chiral activator (0.1 mmol, 1 equiv.), sodiumhydride (60% in mineral oil) (0.22 mmol, 2.2 equiv.), and dry THF (3 mL). The white suspension was stirred and warmed up until everything dissolved and a colour change was observed to give a clear yellow solution. The solution was allowed to cool down to room temperature, after which it was further cooled down to -30 °C using nitromethane/N2 slurry. 1-Hydrosilatrane (2.0 mmol, 2 equiv.) was added to the reaction mixture, followed by the ketone (0.1 mmol). Reaction was stirred for 6 h before it was quenched with 3M HCl (2 mL). Ethyl acetate (1 mL) was added to separate layers, and an aliquot of the top layer was tested using Chiral GC to obtain enantiomeric ratio of product. Product peaks were identified by comparison to GC traces of isolated, and characterized, racemic products. Stereospecificity of peaks were identified by comparison to previously reported data in literature. Aqueous layers from each run were combined with other aqueous layers according to activator used for recycling of activators.
	With C₁₇H₃₈BFeNOP₂; hydrogen In isopropyl alcohol at 70℃; for 3h; Autoclave; Optical yield = 35 %ee;	3.2.1.a 3.2 Hydrogenation of ketones or ketoesters with Iron Complex of example 2.2 General procedure: General procedure:All catalytic hydrogenation experiments using molecular hydrogen were carried out in a Parr Instruments autoclave (300 mL) advanced with an internal alloy plate include up to 8 uniform reaction vials (4 mL) equipped with a cap and needle penetrating the septum.Representative experiment:Under an argon atmosphere, a vial was charged with Iron Complex of example 2.2 whichdissolved in 2 mL of dried solvent. The resulting yellow solution was stuffed briefly beforeketone or ketoester (0,5 or 1 mmol). The vial was placed in the alloy plate which was theninto the autoclave. Once sealed, the autoclave was purged 5 times with hydrogen, then pressurized to 30 bar and heated to desired temperature. Afterwards, the autoclave was cooledRT, depressurized, and the reaction mixture was analyzed by GC-FID or HPLC as well asProduct isolation was performed via column chromatography using silica gel as stationary phase and n-pentane / ethylacetate or n-pentane / acetone mixture as eluent.Individual reaction conditions:[a] 1 mol% cat., 0.5 mmol substrate, 30 bar, 3h, 30 °C, CH2C1 (1,5 mL)[b] 3 mol% cat., 0.5 mmol substrate, 30 bar, 3h, 70 °C, iPrOH (1,5 mL)[c] 2 mol% cat., 0.5 mmol substrate, 30 bar, 2h, 50 °C, EtOH (1,5 mL)[dl 1 mol% cat., 0.5 mmol substrate, 30 bar, 3h, 70 °C, iPrOH (1,5 mL)[f] lmol% cat., 1 mmol substrate, 30 bar, 22h, 40°C, n-heptane (1,5 mL)[g] 1 mol% cat., 1 mmol substrate, 30 bar, 3h, 30 °C, EtOH (2 mL)[h] 1 mol% cat., 1 mmol substrate, 30 bar, 6h, 30 °C, EtOH (2 mL)[i] 1 mol% cat., 1 mmol substrate, 30 bar, 6h, 60 °C, EtOH (2 mL)U] 1 mol% cat., 1 mmol substrate, 30 bar, 6h, 30°C, EtOH (2 mL) [k] 3 mol% cat., 1 mmol substrate, 30 bar, 3h, 70°C, THF (2 mL)SP = side product (Hydrogenation of double bond)
9 % ee	With C₃₀H₃₃BMnN₂O₂P In isopropyl alcohol at 80℃; for 5h; Inert atmosphere; Schlenk technique; enantioselective reaction;
88 % ee	With Lactobacillus paracasei BD₁₀₁ at 28℃; for 24h; Enzymatic reaction;
28 % ee	With whole cell of Weissella paramesenteroides N₇ In water at 20℃; for 24h; Microbiological reaction; Green chemistry; Overall yield = 6 %; enantioselective reaction;
	With C₁₇H₃₈BFeNOP₂; hydrogen In ethanol at 30℃; for 3h; Autoclave; Overall yield = 92 %; Optical yield = 26 %ee; enantioselective reaction;
77 % ee	With 3-[(2S)-2-[(chloro(η⁴-1,5-cyclooctadiene)rhodium)diphenyl phosphanyl]oxy}-3-phenoxypropyl]-1-methyl-1H-imidazol-3-ium chloride; isopropyl alcohol; potassium hydroxide at 82℃; for 3h; Inert atmosphere; Schlenk technique; enantioselective reaction;	General procedure for the asymmetric transfer hydrogenation ofketones General procedure: Typical procedure for the catalytic hydrogen-transfer reaction: asolution of the complexes 3-6 (0.00125 mmol), KOH (0.00625 mmol)and the corresponding ketone (0.25 mmol) in degassed isoPrOH (5 mL)was refluxed until the reaction completed. Then, a sample of the reactionmixture is taken off, diluted with acetone and analyzed immediatelyby GC, conversions obtained are related to the residual unreactedketone
48 % ee	With potassium phosphate; (R)-(+)-1-(4-(dimethylamino)phenyl)ethanol In 1,4-dioxane at 120℃; for 16h; Inert atmosphere; Sealed tube; Overall yield = 44 percent; Overall yield = 8.4 mg;
< 10 % ee	With (S,E)-2-((4-boronobenzylidene)amino)-3-(4-hydroxyphenyl)propanoic acid; isopropyl alcohol; potassium hydroxide at 82℃; for 144h; Schlenk technique;	3.2. General procedure for the transfer hydrogenation of ketones General procedure: Typical procedure for the catalytic hydrogen-transfer reaction:1-4 (0.01 mmol), NaOH (0.05 mmol) and the corresponding ketone(1.00 mmol) in degassed iso-PrOH (10 mL) were refluxed until thereaction completed in a Schlenk tube. After the desired reactiontime, a sample of the reaction mixture is taken off, diluted withacetone and analyzed immediately by GC. Conversion to theproduct was calculated from integration of its GC peak relative tothat of residual unreacted ketone. Furthermore, 1H NMR spectraldata for the resultant products were consistent with previouslyreported results.
72 % ee	With C₄₁H₄₆FeMnN₃O₅P⁽¹⁺⁾*Br^(1-); hydrogen; potassium carbonate In ethanol at 50℃; for 16h; Overall yield = 89 percent; enantioselective reaction;
28 % ee	Stage #1: Cyclohexyl phenyl ketone With ((R)-2'-hydroxy-[1,1'-binaphthalen]-2-yl)diphenylphosphine oxide; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane; lithium diisopropyl amide In 1,4-dioxane at 20℃; for 18h; Inert atmosphere; Schlenk technique; Glovebox; Stage #2: With sodium hydroxide In 1,4-dioxane at 20℃; for 1h; Inert atmosphere; Schlenk technique; Glovebox; Overall yield = 71 percent; Overall yield = 34 mg; enantioselective reaction;
83.3 % ee	With hydrogen; C₄₂H₃₆FeMnN₃O₃P⁽¹⁺⁾*Br^(1-); potassium hydroxide In methanol at 20℃; for 10h; Inert atmosphere; Glovebox; Autoclave; Overall yield = 99 percent; Overall yield = 182.5 mg; enantioselective reaction;	General procedure for hydrogenation of ketones using A as catalyst General procedure: Under an argon atmosphere, a vial was charged with complex A (0.1 mol%) and KOH (2 mol%) which were dissolved in 2 mL of dried MeOH. The resulting red solution was stirred briefly before the ketone (1 mmol) was added. The vial was placed in an alloy plate which was then placed into the autoclave. And the autoclave was purged five times with hydrogen, then pressurized to 30 bars, stirred at room temperature for 10 h. After slowly releasing the hydrogen pressure, the solvent wa sremoved, and the mixture was purified by passing through a short column of silica gel to afford the corresponding alcohol. The ee values of all compounds were determined by HPLC with a chiral column.
28 % ee	With hydrogenchloride; dipotassium hydrogenphosphate; magnesium sulfate heptahydrate; D-glucose; ammonium citrate tribasic In water at 25℃; for 64h; Microbiological reaction; Overall yield = 11 percent; enantioselective reaction;
79 % ee	With bromopentacarbonylmanganese(I); C₅₂H₅₀N₄P₂; isopropyl alcohol; potassium hydroxide at 75℃; for 2h; Inert atmosphere; Schlenk technique; Overall yield = 99 percentSpectr.; enantioselective reaction;	2. Typical procedure for ATH of ketones General procedure: Chiral ligands were synthesized using the procedure we previously reported.1-3 Under a nitrogen atmosphere, the complex [MnBr(CO)5] (2.7 mg, 0.01 mmol), (R,R,R',R')-CyP2N4 (L5) (8.0 mg, 0.01 mmol) were placed in a schlenk tube equipped with a Teflon-coated magnetic stirring bar. Then, iPrOH was added and the mixture was stirred at 55 oC for 30 min. Next, an appropriate amount of KOH/iPrOH solution was added, and the mixture was continually stirred for another 15 min. Later, ketone (0.5 mmol) was introduced, and the mixture was stirred at the desired temperature for the required reaction time. At the end of experiment, 1,3,5-trimethoxybenzene (28.0 mg,0.1667 mmol) as an internal standard was added, the reaction products were determined by GC using a chiralCP-Chiralsil-Dex CB column. Yields were determined by 1H NMR analysis of the crude reaction mixture.

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[45]Durap, Feyyaz; Karakaş, Duygu Elma; Ak, Bünyamin; Baysal, Akin; Aydemir, Murat [Journal of Organometallic Chemistry, 2016, vol. 818, p. 92 - 97]
[46]Meriç, Nermin; Aydemir, Murat [Journal of Organometallic Chemistry, 2016, vol. 819, p. 120 - 128]
[47]Meriç, Nermin; Aydemir, Murat [Journal of Organometallic Chemistry, 2016, vol. 819, p. 120 - 128]
[48]Demmans; Ko; Morris [RSC Advances, 2016, vol. 6, # 91, p. 88580 - 88587]
[49]Baysal, Akın; Elma Karakaş, Duygu; Meriç, Nermin; Ak, Bünyamin; Aydemir, Murat; Durap, Feyyaz [Transition Metal Chemistry, 2017, vol. 42, # 4, p. 365 - 372]
[50]Baysal, Akın; Elma Karakaş, Duygu; Meriç, Nermin; Ak, Bünyamin; Aydemir, Murat; Durap, Feyyaz [Transition Metal Chemistry, 2017, vol. 42, # 4, p. 365 - 372]
[51]Smith, Samantha A. M.; Lagaditis, Paraskevi O.; Lüpke, Anne; Lough, Alan J.; Morris, Robert H. [Chemistry - A European Journal, 2017, vol. 23, # 30, p. 7212 - 7216]
[52]Ramasamy, Balasubramaniyam; Kumar Gangwar, Manoj; Ghosh, Prasenjit [European Journal of Inorganic Chemistry, 2017, vol. 2017, # 26, p. 3253 - 3268]
[53]Current Patent Assignee: UNIVERSITY OF TORONTO - US2016/326202, 2016, A1 Location in patent: Paragraph 0263
[54]Karakaş, Duygu Elma; Aydemir, Murat; Durap, Feyyaz; Baysal, Akın [Inorganica Chimica Acta, 2018, vol. 471, p. 430 - 439]
[55]Meriç, Nermin; Kayan, Cezmi; Gürbüz, Nevin; Karakaplan, Mehmet; Binbay, Nil Ertekin; Aydemir, Murat [Tetrahedron Asymmetry, 2017, vol. 28, # 12, p. 1739 - 1749]
[56]Smith, Samantha A. M.; Prokopchuk, Demyan E.; Morris, Robert H. [Israel Journal of Chemistry, 2017, vol. 57, # 12, p. 1204 - 1215]
[57]Wan, Kai Y.; Roelfes, Florian; Lough, Alan J.; Hahn, F. Ekkehardt; Morris, Robert H. [Organometallics, 2018, vol. 37, # 3, p. 491 - 504]
[58]Wan, Kai Y.; Roelfes, Florian; Lough, Alan J.; Hahn, F. Ekkehardt; Morris, Robert H. [Organometallics, 2018, vol. 37, # 3, p. 491 - 504]
[59]Kayan, Cezmi; Meriç, Nermin; Rafikova, Khadichakhan; Zazybin, Alexey; Gürbüz, Nevin; Karakaplan, Mehmet; Aydemir, Murat [Journal of Organometallic Chemistry, 2018, vol. 869, p. 37 - 47]
[60]Kayan, Cezmi; Meriç, Nermin; Rafikova, Khadichakhan; Zazybin, Alexey; Gürbüz, Nevin; Karakaplan, Mehmet; Aydemir, Murat [Journal of Organometallic Chemistry, 2018, vol. 869, p. 37 - 47]
[61]Varjosaari, Sami E.; Skrypai, Vladislav; Herlugson, Sharon M.; Gilbert, Thomas M.; Adler, Marc J. [Tetrahedron Letters, 2018, vol. 59, # 29, p. 2839 - 2843]
[62]Current Patent Assignee: ROCHE HOLDING AG - WO2018/189060, 2018, A1 Location in patent: Page/Page column 24; 25
[63]Demmans, Karl Z.; Olson, Maxwell E.; Morris, Robert H. [Organometallics, 2018, vol. 37, # 24, p. 4608 - 4618]
[64]Şahin, Engin; Serencam, Hüseyin; Dertli, Enes [Chirality, 2019, vol. 31, # 3, p. 211 - 218]
[65]Tozlu, Caner; Şahin, Engin; Serencam, Hüseyin; Dertli, Enes [Biocatalysis and Biotransformation, 2019, vol. 37, # 5, p. 388 - 398]
[66]Garbe, Marcel; Wei, Zhihong; Tannert, Bianca; Spannenberg, Anke; Jiao, Haijun; Bachmann, Stephan; Scalone, Michelangelo; Junge, Kathrin; Beller, Matthias [Advanced Synthesis and Catalysis, 2019, vol. 361, # 8, p. 1913 - 1920]
[67]Meriç, Nermin; Arslan, Nevin; Kayan, Cezmi; Rafikova, Khadichakhan; Zazybin, Alexey; Kerimkulova, Aygul; Aydemir, Murat [Inorganica Chimica Acta, 2019, vol. 492, p. 108 - 118]
[68]Boit, Timothy B.; Mehta, Milauni M.; Garg, Neil K. [Organic Letters, 2019, vol. 21, # 16, p. 6447 - 6451]
[69]Paşa, Salih; Arslan, Nevin; Meri̇ç, Nermin; Kayan, Cezmi; Bingül, Murat; Durap, Feyyaz; Aydemir, Murat [Journal of Molecular Structure, 2020, vol. 1200]
[70]Widegren, Magnus B.; Clarke, Matthew L. [Catalysis science and technology, 2019, vol. 9, # 21, p. 6047 - 6058]
[71]Carden, Jamie L.; Melen, Rebecca L.; Newman, Paul D.; Ruddy, Adam J.; Willcox, Darren [Dalton Transactions, 2020, vol. 49, # 8, p. 2417 - 2420]
[72]Chen, Jiachen; Hou, Huacui; Ling, Fei; Nian, Sanfei; Wu, Feifei; Xu, Min; Yi, Xiao; Zhong, Weihui [Synlett, 2020, vol. 31, # 3, p. 285 - 289]
[73]Baydaş, Yasemin; Kalay, Erbay; Şahin, Engin [Biocatalysis and Biotransformation, 2022, vol. 40, # 1, p. 29 - 37]
[74]Zhang, Guang-Ya; Ruan, Sun-Hong; Li, Yan-Yun; Gao, Jing-Xing [Chinese Chemical Letters, 2021, vol. 32, # 4, p. 1415 - 1418]

11
[ 603-33-8 ]
[ 2719-27-9 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
95%	With triethylamine; triphenylphosphine In 1,4-dioxane at 80℃; for 4h;
91%	With triethylamine In N,N,N,N,N,N-hexamethylphosphoric triamide at 65℃; for 5h;
79%	With triethylamine In 1,4-dioxane at 80℃; for 3h;

Reference： [1]Rao, Maddali L.N.; Venkatesh, Varadhachari; Jadhav, Deepak N. [Tetrahedron Letters, 2006, vol. 47, # 39, p. 6975 - 6978]
[2]Barton, Derek H. R.; Ozbalik, Nubar; Ramesh, Manian [Tetrahedron, 1988, vol. 44, # 18, p. 5661 - 5668]
[3]Rao, Maddali L.N.; Venkatesh, Varadhachari; Banerjee, Debasis [Tetrahedron, 2007, vol. 63, # 52, p. 12917 - 12926]

12
[ 712-50-5 ]
[ 3132-64-7 ]
[ 6577-70-4 ]

Yield	Reaction Conditions	Operation in experiment
85.1%	With boron trifluoride diethyl etherate at 0 - 5℃; for 7h;	5 S1. Preparation of 2-phenyl-2-cyclohexyl-4-bromomethyl-1,3-dioxolane 0.99 parts by weight of three Boron fluoride ether complex was added dropwise to a dry 65 parts of cyclohexyl phenyl ketone, the temperature was adjusted to 3 ° C, the drop Add dry 34 parts of 1-bromo-2,3-epoxypropane, stirring constantly added dropwise, the temperature was adjusted to 10 ° C, After stirring was continued for 6h, the boron trifluoride diethyl etherate and cyclohexyl phenylmethyl ketone were distilled off under reduced pressure at a temperature of 85 ° C Ketone to give the material A; the material A was added to acetonitrile recrystallization, and dried to give 2-phenyl-2-cyclohexyl-4-bromo Methyl dioxolane
83.8%	With tin(IV) chloride In tetrachloromethane for 2.5h; Ambient temperature;

Reference： [1]Current Patent Assignee: PINGGUANG PHARMACEUTICAL - CN106560469, 2017, A Location in patent: Paragraph 0029; 0034; 0039; 0044; 0049
[2]Sugai; Ikawa; Hasegawa; Yoshida; Kutsuma; Akaboshi [Chemical and Pharmaceutical Bulletin, 1984, vol. 32, # 3, p. 967 - 976]

13
[ 201230-82-2 ]
[ 110-83-8 ]
[ 71-43-2 ]
[ 827-52-1 ]
[ 5454-78-4 ]
[ 712-50-5 ]
[ 98-89-5 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1980,p. 181 - 186

14
[ 712-50-5 ]
[ 2412-73-9 ]

Yield	Reaction Conditions	Operation in experiment
98%	With 2,2'-diperoxyphenic acid In dichloromethane at 20℃; for 24h; Schlenk technique;
	With 3-chloro-benzenecarboperoxoic acid In dichloromethane

Reference： [1]Gan, Shaoyan; Shi, Lei; Song, Lijuan; Yin, Jingru; Yu, Zhiyou [Green Chemistry, 2022, vol. 24, # 5, p. 2232 - 2239]
[2]Momose,T.; Muraoka,O. [Chemical and pharmaceutical bulletin, 1978, vol. 26, p. 2589 - 2593]

15
[ 712-50-5 ]
(S)-cyclohexylphenylmethanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With bis(1,5-cyclooctadiene)diiridium(I) dichloride; formic acid; (αR,2S)-(-)-1-(2-diphenylphosphinobenzyl)-α-(2,2-dimethylpropynyl)-2-pyrrolidinemethanol; potassium carbonate at 40℃; for 6h; Inert atmosphere; Sealed tube; enantioselective reaction;
97%	With sodium tetrahydroborate; G⁽³⁾G amphiphilic dendrimer In tetrahydrofuran for 12h; Ambient temperature;
97%	With sodium tetrahydroborate; third-generation glucose-persubstituted amidoamine dendrimer In tetrahydrofuran at 25℃;

97%	With sodium tetrahydroborate; D-gluconamide PAMAM dendrimer G⁽³⁾G In tetrahydrofuran at 25℃;
97%	Stage #1: Cyclohexyl phenyl ketone With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; Boc-L-alanine(2S)-hydroxypropylamide In tetrahydrofuran; ethanol at 40℃; for 0.25h; Inert atmosphere; Stage #2: With potassium <i>tert</i>-butylate In tetrahydrofuran; ethanol at 40℃; for 24h; Inert atmosphere; enantioselective reaction;
95%	With C₃₆H₄₀Cl₂N₂P₂Ru; potassium <i>tert</i>-butylate In dichloromethane; isopropyl alcohol at 23℃; for 2h; enantioselective reaction;
93%	Stage #1: Cyclohexyl phenyl ketone With (1R,2R)-N,N’-bis(3,5-di-tert-butylbenzyl)-1,2-diphenylethane-1,2-diamine; diethoxymethylane; zinc diacetate In tetrahydrofuran at 25℃; for 24h; Inert atmosphere; Stage #2: With hydrogenchloride; water In tetrahydrofuran for 1h; enantioselective reaction;
93%	Stage #1: Cyclohexyl phenyl ketone With [Ir(COD)2]BF₄; diethoxymethylane; C₂₆H₃₀N₃O₂⁽¹⁺⁾*Cl^(1-) In tetrahydrofuran at 20℃; for 20h; Inert atmosphere; Stage #2: With potassium carbonate In tetrahydrofuran; methanol at 20℃; for 2h; enantioselective reaction;	4.3. General procedure for asymmetric hydrosilane reduction General procedure: To a THF (2 mL) solution of [Ir(cod)2]BF4 (0.02 mmol, 9.9 mg) and azolium salt 1 (0.02 mmol, 9.1 mg) were added propiophenone (4, 0.50 mmol, 67 mg), (EtO)2MeSiH (2.25 mmol, 302 mg). After stirring at room temperature for 20 h under open-air conditions, K2CO3 (2 mg) and MeOH (2 mL) were added. Then, the resulting mixture was stirred at room temperature for 2 h. After evaporation of the solvents, the residue obtained was purified by column chromatography on silica gel (Et2O/n-hexane = 3:7) to give (S)-1-phenyl-1-propanol ((S)-5, 62 mg, 91% isolated yield). The ee was measured by chiral GLC.
92%	With phenylsilane; copper(II) acetate monohydrate; (S)-2,2',6,6'-tetramethoxy-4,4'-bis(di(3,5-xylyl)phosphino)-3,3'-bipyridine In toluene at -20℃; for 60h; enantioselective reaction;
92%	With ammonium iodide; RhH(CO)(PPh<SUB>3</SUB>)<SUB>3</SUB>; C₅₂H₅₈N₄P₂; isopropyl alcohol; potassium hydroxide at 80℃; for 24h; enantioselective reaction;	2.1. Typical procedure for ATH of ketones General procedure: Chiral macrocycles 1 and 2 were synthesized using the same procedure we previously reported [25]. Under air atmosphere, the complex RhH(CO)(PPh3)3 (9.2 mg, 0.01 mmol), (R, R, R', R')-2 (8.0 mg,0.01 mmol), and NH4I (22.0 mg, 0.15 mmol) were placed in a tube equipped with a Teflon-coated magnetic stirring bar. Then, iPrOH was added and the mixture was stirred at 65 °C for 30 min. Next, an appropriate amount of KOH/iPrOH solution was added, and the mixture was continually stirred for another 10 min. Later, ketone was introduced, and the mixture was stirred at the desired temperature for the required reaction time. At the end of experiment, the reaction products were determined by GC using a chiral CP-Chiralsil-Dex CB column.
92%	With Lactobacillus paracasei BD₁₀₁ at 30℃; for 48h; Large scale; Enzymatic reaction; enantioselective reaction;
87%	With silver tetrafluoroborate; diethoxymethylane; C₂₆H₂₉N₃O₂Cl^(1-)Ir⁽¹⁺⁾*C₈H₁₂ at 20℃; for 20h; stereoselective reaction;	2.3.1. Procedure using [IrCl(cod)]2as an Ir catalyst precursor General procedure: A flask was charged with azolium salt L12 (0.02 mmol, 9.1 mg),Ag2O (0.01 mmol, 2.4 mg) and CH2Cl2(1 mL). After stirring the resulting mixture at room temperature for 2 h in the dark, CH2Cl2 was removed in vacuo. Then, a THF (1 mL) solution of [IrCl(cod)]2(0.01 mmol, 6.9 mg) was added to the reaction vessel. The resulting mixture was stirred at room temperature for an additional 4 h in the dark, filtered through a membrane filter, and evaporated to dry-ness in vacuo. Subsequently, to the resulting flask containing yellow solid of the unpurified IrCl(cod)(NHC) complex, a solution of AgBF4(0.025 mmol, 4.9 mg) in CPME (2 mL) was added, and then stirred at room temperature for 1 h. Finally, propiophenone (0.5 mmol,66 mg) and (EtO)2MeSiH (2.25 mmol, 294 mg) were added to the resulting CPME solution (see Appendix A. Supplementary data fordetails). After stirring at room temperature for 20 h under open-air conditions, K2CO3(2 mg) and MeOH (2 mL) were added. Then, the resulting mixture was stirred at room temperature for 2 h. Afterevaporation of the solvents, the residue obtained was purified bycolumn chromatography on silica gel (Et2O/n-hexane = 3:7) to give(S)-1-phenyl-1-propanol (61 mg, 91% isolated yield). The ee was measured by chiral GLC.
47%	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; N-(tert-butoxycarbonyl)-L-valine-(6-amido-1-O-benzyl-6-deoxy-2,3-O-isopropylidene-α-D-mannofuranose); potassium <i>tert</i>-butylate; lithium chloride In tetrahydrofuran; ethanol at 40℃; for 18h; enantioselective reaction;
	With (S)-3,3-dimethyl-butan-2-ol <K salt> In benzene Heating;
	With pyrrolidine; methanol; polymethylhydrosiloxane; (R,R)-ethylenebis(η⁵-tetrahydroindenyl)titanium difluoride; phenylsilane 1.) THF, RT, 2.) THF, 15 deg C, 10 h; Yield given; Multistep reaction;
96 % Chromat.	In isopropyl alcohol at 20℃; for 24.5h;
95 % ee	With bis(1,5-cyclooctadiene)diiridium(I) dichloride; potassium <i>tert</i>-butylate; hydrogen; isopropyl alcohol; (1R,2R)-N-(2-diphenylphosphanylbenzyl)cyclohexane-1,2-diamine In <i>tert</i>-butyl alcohol at 50℃; for 0.5h; Autoclave; Schlenk technique; enantioselective reaction;
91 % ee	With C₂₈H₃₆ClNOP₂Ru; potassium <i>tert</i>-butylate; hydrogen In ethanol at -40℃; for 24h; Autoclave; Inert atmosphere; enantioselective reaction;
	Multi-step reaction with 2 steps 1: (1R,2R)-N,N’-bis(3,5-di-tert-butylbenzyl)-1,2-diphenylethane-1,2-diamine; zinc diacetate / neat (no solvent) / 6 h / 25 °C / Inert atmosphere; Sealed tube 2: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.08 h / 0 °C / Inert atmosphere
97 % ee	With triiron dodecarbonyl; C₄₉H₄₃N₃P₂; potassium hydroxide In isopropyl alcohol at 70℃; for 16h; Inert atmosphere; Glovebox; enantioselective reaction;

Reference： [1]Murayama, Hiroaki; Heike, Yoshito; Higashida, Kosuke; Shimizu, Yohei; Yodsin, Nuttapon; Wongnongwa, Yutthana; Jungsuttiwong, Siriporn; Mori, Seiji; Sawamura, Masaya [Advanced Synthesis and Catalysis, 2020, vol. 362, # 21, p. 4655 - 4661]
[2]Schmitzer; Perez; Rico-Lattes; Lattes [Tetrahedron Letters, 1999, vol. 40, # 15, p. 2947 - 2950]
[3]Schmitzer, Andreea; Perez, Emile; Rico-Lattes, Isabelle; Lattes, Armand [Tetrahedron Asymmetry, 2003, vol. 14, # 23, p. 3719 - 3730]
[4]Schmitzer; Franceschi; Perez; Rico-Lattes; Lattes; Thion; Erard; Vidal [Journal of the American Chemical Society, 2001, vol. 123, # 25, p. 5956 - 5961]
[5]Slagbrand, Tove; Kivijärvi, Tove; Adolfsson, Hans [ChemCatChem, 2015, vol. 7, # 21, p. 3445 - 3449]
[6]Chen, Fumin; He, Dongxu; Chen, Li; Chang, Xiaoyong; Wang, David Zhigang; Xu, Chen; Xing, Xiangyou [ACS Catalysis, 2019, vol. 9, # 6, p. 5562 - 5566]
[7]Szewczyk, Marcin; Stanek, Filip; Bezłada, Agata; Mlynarski, Jacek [Advanced Synthesis and Catalysis, 2015, vol. 357, # 16-17, p. 3727 - 3731]
[8]Teramoto, Hiro; Sakaguchi, Satoshi [Journal of Organometallic Chemistry, 2018, vol. 875, p. 52 - 58]
[9]Qi, Shan-Bin; Li, Min; Li, Shijun; Zhou, Ji-Ning; Wu, Jun-Wen; Yu, Feng; Zhang, Xi-Chang; Chan, Albert S.C.; Wu, Jing [Organic and Biomolecular Chemistry, 2013, vol. 11, # 6, p. 929 - 937]
[10]Zhang, Wen-Jing; Ruan, Sun-Hong; Shen, Wei-Yi; Wang, Zhe; An, Dong-Li; Li, Yan-Yun; Gao, Jing-Xing [Catalysis Communications, 2019, vol. 119, p. 153 - 158]
[11]Şahin, Engin; Serencam, Hüseyin; Dertli, Enes [Chirality, 2019, vol. 31, # 3, p. 211 - 218]
[12]Manabe, Yoshiki; Shinohara, Kanako; Nakamura, Hanako; Teramoto, Hiro; Sakaguchi, Satoshi [Journal of Molecular Catalysis A: Chemical, 2016, vol. 421, p. 138 - 145]
[13]Margalef, Jèssica; Slagbrand, Tove; Tinnis, Fredrik; Adolfsson, Hans; Diéguez, Montserrat; Pàmies, Oscar [Advanced Synthesis and Catalysis, 2016, vol. 358, # 24, p. 4006 - 4018]
[14]Cervinka,O. et al. [Collection of Czechoslovak Chemical Communications, 1967, vol. 32, p. 2618 - 2624]
[15]Yun, Jaesook; Buchwald, Stephen L. [Journal of the American Chemical Society, 1999, vol. 121, # 24, p. 5640 - 5644]
[16]Chen, Jian-Shan; Li, Yan-Yun; Dong, Zhen-Rong; Li, Bao-Zhu; Gao, Jing-Xing [Tetrahedron Letters, 2004, vol. 45, # 45, p. 8415 - 8418]
[17]Fuentes, Jose A.; Carpenter, Ian; Kann, Nina; Clarke, Matthew L. [Chemical Communications, 2013, vol. 49, # 87, p. 10245 - 10247]
[18]Arenas, Ismael; Boutureira, Omar; Matheu, M. Isabel; Díaz, Yolanda; Castillón, Sergio [European Journal of Organic Chemistry, 2015, vol. 2015, # 17, p. 3666 - 3669]
[19]Szewczyk, Marcin; Bezłada, Agata; Mlynarski, Jacek [ChemCatChem, 2016, vol. 8, # 23, p. 3575 - 3579]
[20]Mercadé, Elisabet; Zangrando, Ennio; Clotet, Anna; Claver, Carmen; Godard, Cyril [European Journal of Inorganic Chemistry, 2019, vol. 2019, # 39-40, p. 4211 - 4220]

16
[ 947-19-3 ]
[ 1608-31-7 ]
[ 712-50-5 ]

Reference： [1]Chemical and Pharmaceutical Bulletin,1995,vol. 43,p. 1294 - 1301
[2]Chemical and Pharmaceutical Bulletin,1995,vol. 43,p. 1294 - 1301

17
[ 4335-77-7 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
82%	With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; N,N,N',N'-tetramethylguanidine; In acetonitrile; at 20℃; for 6h;Irradiation;	General procedure: To a 25 mL reaction tube, arylacetic acid (0.2 mmol), 4CzIPN (1 mol%), TMG (50 mol%) were dissolved in CH3CN (1.5 mL), and then the tube was stirred in air at room temperature for 6 h with the irradiation of 25 W blue LEDs. After reaction, the mixture was collected, and the residue was purified by column chromatography on silica gel to afford the desired products.

Reference： [1]Journal of Organic Chemistry,2014,vol. 79,p. 1867 - 1871
[2]Green Chemistry,2019,vol. 21,p. 6187 - 6193
[3]Tetrahedron Letters,1998,vol. 39,p. 3327 - 3330
[4]Tetrahedron,2001,vol. 57,p. 1075 - 1081
[5]Chinese Chemical Letters,2019

18
[ 712-50-5 ]
[ 100-49-2 ]

Reference： [1]Tetrahedron,1999,vol. 55,p. 7441 - 7460

19
[ 712-50-5 ]
ZnCl₂ [ No CAS ]
[ 827-52-1 ]

Reference： [1]Bulletin de la Societe Chimique de France,1936,vol. <5> 3,p. 239,247
Chemisches Zentralblatt,1937,vol. 108,p. 2585

20
[ 98-89-5 ]
[ 98-80-6 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
81%	Stage #1: Cyclohexanecarboxylic acid With di(succinimido) carbonate; sodium carbonate; tricyclohexylphosphine In tetrahydrofuran at 60℃; Stage #2: phenylboronic acid In tetrahydrofuran at 60℃; for 20h; Further stages.;
65%	With 1,1'-bis-(diphenylphosphino)ferrocene; water; dimethyl dicarbonate In tetrahydrofuran at 50℃; for 16h;
60%	With palladium diacetate; P(p-CH₃OC₆H₄)3; 2,2-dimethylpropanoic anhydride In 1,2-dimethoxyethane; water at 60℃; for 16h;

60%

With P(p-CH₃OC₆H₄)3; 2,2-dimethylpropanoic anhydride In tetrahydrofuran; water at 60℃; for 16h;

Reference： [1]Goossen; Ghosh [Chemical Communications, 2001, # 20, p. 2084 - 2085]
[2]Gooßen, Lukas J.; Winkel, Lars; Döhring, Arno; Ghosh, Keya; Paetzold, Jens [Synlett, 2002, # 8, p. 1237 - 1240]
[3]Gossen, Lukas J.; Ghosh, K. [Angewandte Chemie - International Edition, 2001, vol. 40, # 18, p. 3458 - 3460][Angewandte Chemie, 2001, vol. 40, # 18, p. 3458 - 3468]
[4]Goossen, Lukas J.; Ghosh, Keya [European Journal of Organic Chemistry, 2002, # 19, p. 3254 - 3267]

21
[ 712-50-5 ]
[ 23459-35-0 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: Cyclohexyl phenyl ketone With ammonium acetate In methanol at 25℃; for 0.166667h; Stage #2: With sodium cyanoborohydride In methanol at 60℃; for 16h; Stage #3: With sodium hydroxide In water	4.2.54.1 Cyclohexyl(phenyl)methanamine Cyclohexyl(phenyl)methanone (940 mg, 5 mmol) was dissolved in MeOH (15 mL) and then NH4OAc (4.62 g, 60 mmol) was added. Reaction was stirred for 10 min at 25 °C. NaBH3CN (1.26 g, 20 mmol) was added and the reaction was heated to 60 °C and stirred at that temperature for 16 h. The solvent was removed under reduced pressure and the reaction mixture was suspended in 0.5 M aq NaOH (75 mL), extracted with EtOAc (3 × 20 mL), dried (MgSO4) and then under reduced pressure to give the title compound as a clear oil (868 mg, 92%). 1H NMR (400 MHz, CDCl3) δ ppm 7.20-7.41 (m, 5H), 3.61 (d, J = 7.78 Hz, 1H), 2.77 (br s, 2H), 1.96 (d, J = 12.80 Hz, 1H), 1.78 (d, J = 13.05 Hz, 1H), 1.47-1.70 (m, 3H), 1.38 (d, J = 12.30 Hz, 1H), 0.78-1.33 (m, 5H).
90%	With ammonia; hydrogen In ethanol at 100℃; for 9h; Autoclave; Sealed tube; Inert atmosphere;	1.1 1) Preparation of α-cyclohexylbenzylamine 1000 ml autoclave, 94 g of cyclohexylphenyl ketone was added, 600 ml of anhydrous ethanol 12g catalyst KT-02, Sealed reactor, With a vacuum pump to remove the air inside the kettle, And then filled with nitrogen to 0.5MPa, And then vacuum pump vacuum; Negative pressure conditions filled with 80g ammonia, Charge ammonia is completed, The autoclave was filled with hydrogen to 4 MPa, And the temperature was raised to 100 ° C to carry out the reaction. After 9 hours of reaction, Found no longer absorb hydrogen, The reaction is stopped. When the temperature of the system is reduced to room temperature, The reaction solution is filtered, Concentrated α-cyclohexylbenzylamine crude. The crude product in the case of mixing, Added to dilute hydrochloric acid solution, Let it react to produce α-cyclohexylbenzylamine salt, And dissolved in aqueous solution, And taking ethyl acetate as an aqueous solution to remove organic impurities, After dispensing, Keep the water phase, After the water phase is extracted twice with ethyl acetate, With sodium hydroxide to adjust the pH to alkaline, And then ethyl acetate 3 times, At this time, the extracted ethyl acetate phase was collected after adjusting the pH, Dried and concentrated, α-cyclohexylbenzylamine obtained pure 85.0g, The yield was 90.0% And the purity was 99.3% by HPLC.
72%	Stage #1: Cyclohexyl phenyl ketone With titanium(IV) isopropylate; ammonia In ethanol at 25℃; for 6h; Stage #2: With sodium tetrahydroborate In ethanol at 25℃; for 3h; Further stages.;

	With ammonium acetate; sodium cyanoborohydride In methanol at 20℃; for 168000h;
	Multi-step reaction with 2 steps 1: formic acid / 8 h / 180 °C 2: conc. HCl / 1 h / Heating
	Multi-step reaction with 2 steps 1: 1.) NH₃ (g), Ti(O-iPr)4; 2.) TiCl₄ / diethyl ether; pentane / 1 h / 0 °C 2: borane-dimethyl sulfide complex / diethyl ether / 0 deg C -> room temp. for 14 h
99 % ee	With ((-)-(1S)-[1,1'-binaphthalene]-2,2'-diylbis[diphenylphosphine-κP])chloro[(1,2,3,4,5,6-η)-1-methyl-4-(1-methylethyl)benzene]ruthenium(1+) chloride; ammonia; hydrogen; ammonium chloride In methanol; water at 90℃; for 48h; Autoclave; Inert atmosphere; enantioselective reaction;	13 General procedure: General procedure for the asymmetric reductive amination using ammonium chloride as the ammonium salt.All manipulations were done under an atmosphere of nitrogen. The methanol and water were deoxygenated by 5 vacuum/nitrogen cycles prior to use.The reactions were carried out in small autoclaves that can be pressurized to 50 bar. To a 2OmL glass vial is added immol of the oxime, 0,O2Smmol of preformed catalyst, lOmmol NH4CI and 2mL degassed methanol, immol NH3 (added as a 7M solution in methanol) and 20iiL water. The glass vial is put into the parallel autoclave under an atmosphere of nitrogen gas and 40 bar of hydrogen is applied and the autoclave is heated to 90°C and agitated. After 48 hours the autoclave is cooled to 20°C and then the hydrogen pressure is released. The methanol is evaporated off and NaOH(aq) is added to the residue to pH>11. The mixture is extracted with diethylether. The combined ether fractions are dried over MgSO4, filtered and concentrated under vacuum to afford the amine product. The products were analyzed by chiral HPLC and 1H and 13C NMR spectroscopy and were in accordance with authentic samples.Small scale reactions using various ligands.The reactions were carried out according to the procedure described above but at smaller scale.
	Multi-step reaction with 2 steps 1: hydroxylamine hydrochloride; sodium acetate / ethanol / 6 h / 60 °C 2: hydrogenchloride; palladium 10% on activated carbon; hydrogen / ethanol; water

Reference： [1]Laufer, Radoslaw; Ng, Grace; Liu, Yong; Patel, Narendra Kumar B.; Edwards, Louise G.; Lang, Yunhui; Li, Sze-Wan; Feher, Miklos; Awrey, Don E.; Leung, Genie; Beletskaya, Irina; Plotnikova, Olga; Mason, Jacqueline M.; Hodgson, Richard; Wei, Xin; Mao, Guodong; Luo, Xunyi; Huang, Ping; Green, Erin; Kiarash, Reza; Lin, Dan Chi-Chia; Harris-Brandts, Marees; Ban, Fuqiang; Nadeem, Vincent; Mak, Tak W.; Pan, Guohua J.; Qiu, Wei; Chirgadze, Nickolay Y.; Pauls, Henry W. [Bioorganic and Medicinal Chemistry, 2014, vol. 22, # 17, p. 4968 - 4997]
[2]Current Patent Assignee: Wang, Jiju - CN106397217, 2017, A Location in patent: Paragraph 0006; 0009
[3]Miriyala, Bruhaspathy; Bhattacharyya, Sukanta; Williamson, John S. [Tetrahedron, 2004, vol. 60, # 7, p. 1463 - 1471]
[4]Sasse, Astrid; Ligneau, Xavier; Rouleau, Agnès; Elz, Sigurd; Ganellin, C. Robin; Arrang, Jean-Michel; Schwartz, Jean-Charles; Schunack, Walter; Stark, Holger [Journal of Medicinal Chemistry, 2002, vol. 45, # 18, p. 4000 - 4010]
[5]Ho, Bin; Michael Crider; Stables, James P [European Journal of Medicinal Chemistry, 2001, vol. 36, # 3, p. 265 - 286]
[6]Johansson, Anders; Lindstedt, Eva-Lotte; Olsson, Thomas [Acta Chemica Scandinavica, 1997, vol. 51, # 3, p. 351 - 353]
[7]Current Patent Assignee: GOVERNMENT OF SWEDEN; RISE (in: Government of Sweden) - WO2015/178846, 2015, A1 Location in patent: Page/Page column 5; 6
[8]Current Patent Assignee: CHINESE ACADEMY OF MEDICAL SCIENCES - JP2015/172077, 2015, A

22
[ 712-50-5 ]
[ 2065-66-9 ]
[ 5700-44-7 ]

Yield	Reaction Conditions	Operation in experiment
92%	With n-butyllithium In tetrahydrofuran at 0 - 20℃; for 8h;
80%	Stage #1: methyl-triphenylphosphonium iodide With n-butyllithium In tetrahydrofuran; hexane at 0℃; Inert atmosphere; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran; hexane at -78 - 20℃; for 3.83333h; Inert atmosphere;
	Stage #1: methyl-triphenylphosphonium iodide With n-butyllithium In tetrahydrofuran; hexane at 0 - 20℃; for 0.25h; Stage #2: Cyclohexyl phenyl ketone at 20℃; for 8h; Stage #3: With ammonium chloride	1 EXAMPLE 1 To a suspension of methyltriphenylphosphonium iodide in dry THF at ambient temperature was added n-BuLi (2M soln in hexane).After stirring for 15 minutes at 0° C., cyclohexylphenyl ketone was added.The reaction mixture was stirred for 8 h at ambient temperature and then quenched with aqueous ammonium chloride and extracted with ethyl acetate.The combined organic phases were washed (brine), dried (Na2SO4) and concentrated.Silica gel column chromatography of the crude product using petroleum ether:EtOAc (49:1) as eluent gave α-cyclohexylstyrene as a colorless oil. To a mixture of K3Fe(CN)6, K2CO3 and Hydroquininel,4,-phthalazinediyldiether (DHQ)2PHAL in t-BuOH-H2O (1:1) cooled to 0° C. was added OsO4 (0.1M solution in toluene). After stirring for 5 minutes at 0° C., α-cyclohexylstyrene was added in one portion. The reaction mixture was stirred at 0° C. for 18 h and then quenched with solid sodium sulfite. The stirring was continued for 1 h and the solution was extracted with ethyl acetate. The combined organic phases were washed (brine), dried (Na2SO4) and concentrated. Silica gel column chromatography of crude product using petroleum ether:EtOAc (4:1) as eluent gave (S)-1-cyclohexyl-1-phenyl-1,2-ethanediol as a white solid. [0041] To a solution of oxalyl chloride in dry dichloromethane cooled at -78° C. was added dry DMSO in dichloromethane and stirred for 20 min. The solution of (S)-1-cyclohexyl-1-phenyl-1,2-ethanediol in dichloromethane was added at -60° C. and stirred for 30 min. A solution of triethylamine in dichloromethane was added and stirred for 1 h. The reaction was allowed to warm to ambient temperature and poured into 2N HCl and extracted with dichloromethane. The combined organic layers were washed (brine), dried (Na2SO4) and concentrated to give the virtually pure aldehyde as a pale yellow solid. [0042] To the solution of above aldehyde in t-BuOH at 0° C. was added an aqueous solution of NaCIO2 and NaH2PO4.2H2O. The yellow solution was stirred at ambient temperature for 4 h and then quenched with solid Na2SO3. The reaction mixture was acidified with HCl and extracted with dichloromethane. The combined organic phases were washed (brine), dried (Na2SO4) and concentrated. Silica gel column chromatography of the crude acid with chloroform:MeOH (9:1) gave the (S)-cyclohexylphenyl glycolic acid as a white solid. This was recrystallized from petroleum ether:ether.

	Stage #1: methyl-triphenylphosphonium iodide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 15h; Stage #2: Cyclohexyl phenyl ketone With ammonium chloride In water at 20℃; for 8h;	4 EXAMPLE 4 To a mixture of K3Fe(CN)6) K2CO3 and (DHQD)2PHAL in t-BuOH-H2O (1:1) cooled to 0° C. was added OsO4 (0.1M solution in toluene). After stirring for 5 minutes at 0° C., α-cyclohexylstyrene was added in one portion. The reaction mixture was stirred at 0° C. for 18 h and then quenched with solid sodium sulfite. The stirring was continued for 1 h and the solution was extracted with ethyl acetate. The combined organic phases were washed brine), dried (Na2SO4) and concentrated. Silica gel column chromatography of crude product using petroleum ether:EtOAc (4:1) as eluent gave (R)-1-cyclohexyl-1-phenyl-1,2-ethanediol as a white solid. [0053] To a suspension of pyridinium dichromate in dry dichloromethane cooled at 0° C. was added a solution of (R)-1-cyclohexyl-1-phenyl-1,2-ethanediol in dichloromethane and stirred for 3 h. The reaction mixture was then diluted with ether and filtered. The filtrate was concentrated to give the virtually pure aldehyde as a pale yellow solid. [0054] To the solution of above aldehyde in t-BuOH at 0° C. was added an aqueous solution of NaCIO2 and NaH2PO4.2H2O. The yellow solution was stirred at ambient temperature for 4 h and then quenched with solid Na2SO3. The reaction mixture was acidified with HCl and extracted with dichloromethane. The combined organic phases were washed (brine), dried (Na2SO4) and concentrated. Silica gel column chromatography of the crude acid with chloroform:MeOH (9:1) gave the (R)-cyclohexylphenyl glycolic acid as a white solid. This was recrystalized from petroleum ether:ether.
	Stage #1: methyl-triphenylphosphonium iodide With sodium amide In tetrahydrofuran at 0 - 20℃; for 15h; Stage #2: Cyclohexyl phenyl ketone With ammonium chloride In water at 20℃; for 8h;	2 EXAMPLE 2 To a suspension of methyltriphenylphosphonium iodide in dry THF cooled at 0° C. was added NaNH2.After stirring for 15 h at ambient temperature, cyclohexylphenyl ketone was added.The reaction mixture was stirred for 8 h at ambient temperature and then quenched with aqueous ammonium chloride and extracted with ethyl acetate.The combined organic phases were washed (brine), dried (Na2SO4) and concentrated.Silica gel column chromatography of the crude product using petroleum ether:EtOAc (49:1) as eluent gave α-cyclohexylstyrene as a colorless oil. To a mixture of K3Fe(CN)6, K2CO3 and (DHQ)2PHAL in t-BuOH:H2O (1:1) cooled to -15° C. was added OSO4 (0.1M solution in toluene). After stirring for 5 minutes at 0° C., α-cyclohexylstyrene was added in one portion. The reaction mixture was stirred at 0° C. for 18 h and then quenched with solid sodium sulfite. The stirring was continued for 1 h and the solution was extracted with ethyl acetate. The combined organic phases were washed (brine), dried (Na2SO4) and concentrated. Silica gel column chromatography of crude product using petroleum ether:EtOAc (4:1) as eluent gave (S)-1-cyclohexyl-1-phenyl-1,2-ethanediol as a white solid. [0045] To a suspension of phosphorus pentoxide in dry dichloromethane cooled at 0° C. was added dry DMSO in dichloromethane and stirred for 20 min. The solution of (S)-1 cyclohexyl-1-phenyl-1,2-ethanediol in dichloromethane was added at 0° C. and stirred for 30 min. A solution of triethylamine in dichloromethane was added and stirred for 1 h. The reaction was allowed to warm to ambient temperature and poured into 2N HCl and extracted, with dichloromethane. The combined organic layers were washed (brine), dried (Na2SO4) and concentrated to give the virtually pure aldehyde as a pale yellow solid. [0046] To the solution of above aldehyde in t-BuOH at 0° C. was added an aqueous solution of KClO2 and NaH2PO4.2H2O. The yellow solution was stirred at ambient temperature for 4 h and then quenched with solid Na2SO3. The reaction mixture was acidified with HCl and extracted with dichloromethane. The combined organic phases were washed (brine), dried (Na2SO4) and concentrated. Silica gel column chromatography of the crude acid with chloroform:MeOH (9:1) gave the (S)-cyclohexylphenyl glycolic acid as a white solid. This was recrystallized from petroleum ether:ether.
	Stage #1: methyl-triphenylphosphonium iodide With sodium hexamethyldisilazane In tetrahydrofuran at 0℃; for 0.25h; Stage #2: Cyclohexyl phenyl ketone With ammonium chloride at 20℃; for 8h;	3 EXAMPLE 3 To a suspension of methyltriphenylphosphonium iodide in dry THF cooled at 0° C. was added NaHMDS (1M soln in THF).After stirring for 15 minutes at 0° C., cyclohexylphenyl ketone was added in one portion.The reaction mixture was stirred for 8 h at ambient temperature and then quenched with aqueous ammonium chloride and extracted with ethyl acetate.The combined organic phases were washed (brine), dried (Na2SO4) and concentrated.Silica gel column chromatography of the crude product using petroleum ether:EtOAc (49:1) as eluent gave α-cyclohexylstyrene as a colorless oil.To a mixture of K3Fe(CN)6, K2CO3 and (DHQ)2PHAL in t-BuOH-H2O (1:1) at ambient temperature was added OsO4 (0.1M solution in toluene). After stirring for 5 minutes at 0° C., α-cyclohexylstyrene was added in one portion. The reaction mixture was stirred at 0° C. for 18 h and then quenched with solid sodium sulfite. The stirring was continued for 1 h and the solution was extracted with ethyl acetate. The combined organic phases were washed (brine), dried (Na2SO4) and concentrated. Silica gel column chromatography of crude product using petroleum ether:EtOAc (4:1) as eluent gave (S)-1-cyclohexyl-1-phenyl-1,2-ethanediol as a white solid. [0049] To a solution of trifluoroacetic anhydride in dry dichloromethane cooled at -78° C. was added dry DMSO in dichloromethane and stirred for 20 min. The solution of (S)-1-cyclohexyl-1-phenyl-1,2-ethanediol in dichloromethane was added at -60° C. and stirred for 30 min. A solution of diisopropylethyl amine in dichloromethane was added and stirred for 1 h. The reaction was allowed to warm to ambient temperature and poured into 2N HCl and extracted with dichloromethane. The combined organic layers were washed (brine), dried (Na2SO4) and concentrated to give the virtually pure aldehyde as a pale yellow solid. [0050] To the solution of above aldehyde in t-BuOH at 0° C. was added an aqueous solution of TEMPO. The yellow solution was stirred at ambient temperature for 4 h and then quenched with solid (Na2SO4). The reaction mixture was acidified with HCl and extracted with dichloromethane. The combined organic phases were washed (brine), dried (Na2SO4) and concentrated. Silica gel column chromatography of the crude acid with chloroform:MeOH (9:1) gave the (S)-cyclohexylphenyl glycolic acid as a white solid. This was recrystallized from petroleum ether:ether.

Reference： [1]Gupta, Priti; Fernandes, Rodney A.; Kumar, Pradeep [Tetrahedron Letters, 2003, vol. 44, # 22, p. 4231 - 4232]
[2]Monfette, Sebastien; Turner, Zoe R.; Semproni, Scott P.; Chirik, Paul J. [Journal of the American Chemical Society, 2012, vol. 134, # 10, p. 4561 - 4564]
[3]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - US2004/192962, 2004, A1 Location in patent: Page 3
[4]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - US2004/192962, 2004, A1 Location in patent: Page 4
[5]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - US2004/192962, 2004, A1 Location in patent: Page 3
[6]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - US2004/192962, 2004, A1 Location in patent: Page 3

23
[ 7677-24-9 ]
[ 712-50-5 ]
[ 503183-77-5 ]
(R)-cyclohexyl(phenyl)[(trimethylsilyl)oxy]acetonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
39%	In propiononitrile at -60 - -40℃; for 216h;	1; 2 EXAMPLE 1 There is first examined a ligand 1-L in which R1 to R3 in the formula (I) are at nonexistent state and each of R4 and R5 is a hydrogen atom. [0049] [3-benzyloxy-4-(2-methoxyphenyl)-tetrahydro-pyrano[3,2-d][1,3]dioxyn-8-al alcohol (is rendered into sodium alkoxide and subjected to a nucleophilic displacement reaction with an arene chromium complex to obtain 8-(2-methoxyphenyl)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxyn (hereinafter referred to as compound 2) in which a catechol portion is introduced into a hydroxyl group of the alcohol. The compound 2 is reduced with DIBAL-H to form [3-benzyloxy-4-(2-methoxyphenyl)-tetrahydro-pyran-2-yl]methanol (hereinafter referred to as compound 3). The compound 3 is subjected to a tosylation to obtain toluene-4-sulfonic acid 3-benzyloxy-4-(2-methoxyphenyl)-tetrahydro-pyran-2-yl-methylester (hereinafter referred to as compound 4). The compound 4 is reacted with Ph2PK and oxidized with H2O2 to form 3-benzyloxy-2-(diphenyl phosphinoylmethyl)-4-(2-methoxyphenyl)-tetrahydro-pyran (hereinafter referred to as compound 5). The compound 5 is subjected to a reduction debenzylation with palladium (Pd/C) catalyst and further to deblocking of methyl ether with AlC13-EtSH to obtain a ligand 1-L. [0050] The values of physical properties of the thus obtained ligand 1-L are shown below. [0051] Melting point: 219-220 C. [0052] 1H-NMR (500 MHz. CDCl3) d1.94 (m, 1H), 2.14 (m, 1H), 2.69 (ddd, J=9.8, 15.0, 15.0 Hz, 1H), 2.84 (ddd, J=2.8, 9.5, 15.3 Hz, 1H), 3.23 (ddd, J=1.9, 12.2, 12.2 Hz, 1H), 3.34 (dddd, J=2.8, 7.0, 9.4, 9.8 Hz, 1H), 3.55 (ddd, J=5.5, 8.9, 11.6 Hz, 1H), 3.73 (dd, J=8.9, 9.4 Hz, 1H), 3.90(ddd, J=1.2, 5.7, 12.2 Hz, 1H), 6.71 (ddd, J=1.9, 7.4, 7.4 Hz, 1H), 6.96 (m, 3H), 7.51 (m, 6H), 7.75 (m, 4H), 8.92 (s, 1H); 13C-NMR (125 MHz, CDCl3) d31.62, 37.61(d, J=68 Hz), 65.50, 74.96, 76.11, 84.84, 117.22, 119.14, 122.45, 125.50, 128.90, 129.00, 129.03, 129.13, 130.60(d, J=10 Hz), 131.11(d, J=9 Hz), 132.47, 145.89, 150.15; 31P- NMR (202 MHz, CDCl3), d34.0 [0053] IR 3422, 1156, 1103 cm-1 [0054] Analytical value as C25H27O5P: C, 67.67; H, 6.10%. 02070 (2002-157,290) [0055] Found value: C, 67.92; H, 5.94% [0056] Next, it is tried to synthesize an oxybutynin derivative by using the above ligand. The synthesis root is shown as follows. [CHEMMOL-00006] [0057] A commercially available cyclohexyl phenylketone is subjected to a cyanosilylation at -60 C. or -40 C. using 5 or 1 mol % of (S)-selective catalyst prepared by mixing Gd(OiPr)3 and the ligand 1-L at a mixing ratio of 1:2 for 32 hours. After the completion of the reaction, an objective cyanohydrin is obtained in a yield of 96-100% and an enantiomer excess of 94%ee. In this case, TMS(tetramethylsilane)CN (120 mol %) is used as a silylcyanide, and propionitrile is used as a solvent. [0058] The spectrum data of (S)-cyanohydrin are shown as follows: [0059] 1H-NMR 0.09 (s, 9H), 1.02-1.21 (m, 5H), 1.35-1.39 (m, 1H), 1.62-1.65 (m, 1H), 1.68-1.75 (m, 2H), 1.79-1.82 (m, 1H), 1.99-2.03 (m, 1H), 7.32-7.39 (m, 3H), 7,45-7.47 (m, 2H) [0060] Then, the cyanohydrin is reduced with diisobutyl aluminum hydride (in CH2Cl2 solvent, -78 C., 8 hours) and oxidized with sodium chlorite to obtain a basic skeleton of oxybutynin in a yield of 36-68%.There are examined a ligand 2 in which each of R1-R3 and R5 in the formula (I) is a hydrogen atom and R4 is a fluorine atom, and a ligand 3 in which each of R1-R3 and R5 in the formula (I) is a hydrogen atom and R4 takes a closed ring structure. The same experiment as in Example 1 is carried out to try the production of a basic skeleton of an oxybutynin. The results are shown in Table 1. In Table 1, ee represents an enantiomer excess. As seen from Table 1, the ligand 1 attains excellent yield and enantiomer excess even when the concentration of the asymmetric catalyst is properly changed. Similarly, the good results are obtained even in the ligands 2 and 3. [0063] The basic skeleton of oxybutynin is prepared by using these ligands in the same manner as in Example 1, respectively. As a result, any skeletons are obtained in a yield of 36-68%.
	With chiral gadolinium(III)-phosphine oxide In various solvent(s) at -40℃; for 40h; Title compound not separated from byproducts;

Reference： [1]Current Patent Assignee: THE UNIVERSITY OF TOKYO - US2004/6243, 2004, A1 Location in patent: Page 4
[2]Masumoto, Shuji; Suzuki, Masato; Kanai, Motomu; Shibasaki, Masakatsu [Tetrahedron, 2004, vol. 60, # 46 SPEC. ISS., p. 10497 - 10504]

24
[ 712-50-5 ]
(R)-cyclohexylphenylmethanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With potassium <i>tert</i>-butylate; hydrogen In isopropyl alcohol at 25℃; for 18h;
99%	With 1,1,1,3',3',3'-hexafluoro-propanol; C₃₂H₃₉BrMnN₂O₂P; potassium <i>tert</i>-butylate; hydrogen In methanol at 20℃; for 16h; Glovebox; Autoclave; enantioselective reaction;
97.6%	With C₄₈H₆₆FeN₆P₂⁽²⁺⁾*2BF₄^(1-); sodium t-butanolate In isopropyl alcohol at 75℃; for 1h; Glovebox; Schlenk technique; enantioselective reaction;

97%	With C₃₇H₄₀MnN₂O₂P₂⁽¹⁺⁾*Br^(1-); sodium t-butanolate In isopropyl alcohol at 50℃; for 3h; Inert atmosphere; Schlenk technique; enantioselective reaction;
94%	With ammonium iodide; RhH(CO)(PPh<SUB>3</SUB>)<SUB>3</SUB>; C₅₂H₅₈N₄P₂; isopropyl alcohol; potassium hydroxide at 65℃; for 4h; enantioselective reaction;	2.1. Typical procedure for ATH of ketones General procedure: Chiral macrocycles 1 and 2 were synthesized using the same procedure we previously reported [25]. Under air atmosphere, the complex RhH(CO)(PPh3)3 (9.2 mg, 0.01 mmol), (R, R, R', R')-2 (8.0 mg,0.01 mmol), and NH4I (22.0 mg, 0.15 mmol) were placed in a tube equipped with a Teflon-coated magnetic stirring bar. Then, iPrOH was added and the mixture was stirred at 65 °C for 30 min. Next, an appropriate amount of KOH/iPrOH solution was added, and the mixture was continually stirred for another 10 min. Later, ketone was introduced, and the mixture was stirred at the desired temperature for the required reaction time. At the end of experiment, the reaction products were determined by GC using a chiral CP-Chiralsil-Dex CB column.
89%	With [Fe(II)(N-isocyano-N-isopropylpropan-2-amine)₂((5S,8S,14aS,18aS)-5,8-diphenyl-5,6,7,8,13,14,14a,15,16,17,18,18a,19,20-tetradecahydrotribenzo[b,f,l][1,4]diaza[8,11]diphosphacyclotetradecine)](BF₄)₂; isopropyl alcohol; sodium t-butanolate at 75℃; for 5h; Glovebox; enantioselective reaction;
63%	With triiron dodecarbonyl; C₅₂H₅₈N₄P₂; hydrogen; potassium hydroxide In methanol at 45℃; for 10h; enantioselective reaction;
32%	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; N-(tert-butoxycarbonyl)-L-valine-(6-O-benzoyl-1-O-benzyl-5-deoxy-2,3-O-isopropylidene-5-thioamido-α-D-mannofuranose); potassium <i>tert</i>-butylate; lithium chloride In tetrahydrofuran; isopropyl alcohol at 20℃; for 3h; enantioselective reaction;
98 % Chromat.	In isopropyl alcohol at 20℃; for 2h;
	With potassium hydroxide In isopropyl alcohol at 25℃; for 22h;
97 %Chromat.	With C₄₉H₆₈FeN₆P₂⁽²⁺⁾*2BF₄^(1-); sodium t-butanolate In isopropyl alcohol at 75℃; for 1h; enantioselective reaction;
99 %Chromat.	With bis(triphenylphosphine)carbonyliridium(I) chloride; C₇₀H₇₃N₄P₃; potassium hydroxide In isopropyl alcohol at 40℃; for 0.5h; Inert atmosphere; enantioselective reaction;	2.2. Typical procedure for ATH General procedure: Under nitrogen atmosphere, the catalyst precursor IrCl(-CO)(PPh3)2 (3.9 mg, 0.005 mmol) and (R,R,R,R)-3 (5.3 mg,0.005 mmol) were placed in a tube equipped with a Teflon-coated magnetic stirring bar. i-PrOH was then added and the mixture was stirred at 40 8C for 20 min. An appropriate amount of KOH/i-PrOH solution was then added, and the mixture was continually stirredfor another 20 min. Next, ketone (0.5 mmol) was introduced and the mixture was stirred at 40 8C for the required reaction time. At the end of the reaction, the product was analyzed by GC using achiral CP-Chirasil-Dex CB column.
	Multi-step reaction with 3 steps 1: hydrogen / methanol / 9 h / 90 °C / 30003 Torr / Autoclave 2: porcine pancreatic lipase / toluene / 12 h / 40 °C / Enzymatic reaction 3: lithium hydroxide / tetrahydrofuran / 20 °C

Reference： [1]Huang, Hanmin; Okuno, Tomoko; Tsuda, Kazuomi; Yoshimura, Masahiro; Kitamura, Masato [Journal of the American Chemical Society, 2006, vol. 128, # 27, p. 8716 - 8717]
[2]Zhang, Linli; Tang, Yitian; Han, Zhaobin; Ding, Kuiling [Angewandte Chemie - International Edition, 2019, vol. 58, # 15, p. 4973 - 4977][Angew. Chem., 2019, vol. 131, p. 5027 - 5031,5]
[3]Bigler, Raphael; Huber, Raffael; Mezzetti, Antonio [Angewandte Chemie - International Edition, 2014, vol. 54, # 17, p. 5171 - 5174][Angew. Chem., 2014, vol. 127, # 17, p. 5260 - 5263,4]
[4]Passera, Alessandro; Mezzetti, Antonio [Angewandte Chemie - International Edition, 2020, vol. 59, # 1, p. 187 - 191][Angew. Chem., 2020, vol. 132, p. 193 - 197,5]
[5]Zhang, Wen-Jing; Ruan, Sun-Hong; Shen, Wei-Yi; Wang, Zhe; An, Dong-Li; Li, Yan-Yun; Gao, Jing-Xing [Catalysis Communications, 2019, vol. 119, p. 153 - 158]
[6]Bigler, Raphael; Mezzetti, Antonio [Organic Process Research and Development, 2016, vol. 20, # 2, p. 253 - 261]
[7]Li, Yanyun; Yu, Shenluan; Wu, Xiaofeng; Xiao, Jianliang; Shen, Weiyi; Dong, Zhenrong; Gao, Jingxing [Journal of the American Chemical Society, 2014, vol. 136, # 10, p. 4031 - 4039]
[8]Margalef, Jèssica; Slagbrand, Tove; Tinnis, Fredrik; Adolfsson, Hans; Diéguez, Montserrat; Pàmies, Oscar [Advanced Synthesis and Catalysis, 2016, vol. 358, # 24, p. 4006 - 4018]
[9]Chen, Jian-Shan; Li, Yan-Yun; Dong, Zhen-Rong; Li, Bao-Zhu; Gao, Jing-Xing [Tetrahedron Letters, 2004, vol. 45, # 45, p. 8415 - 8418]
[10]Zhang, Xue-Qin; Li, Yan-Yun; Zhang, Hui; Gao, Jing-Xing [Tetrahedron Asymmetry, 2007, vol. 18, # 17, p. 2049 - 2054]
[11]Bigler, Raphael; Huber, Raffael; Stöckli, Marco; Mezzetti, Antonio [ACS Catalysis, 2016, vol. 6, # 10, p. 6455 - 6464]
[12]Tao, Meng; Wu, Fang; Li, Teng; Li, Yan-Yun; Gao, Jing-Xing [Chinese Chemical Letters, 2017, vol. 28, # 1, p. 97 - 100]
[13]Current Patent Assignee: ANHUI AIYOUCHENG BIOLOGICAL TECH - CN106397117, 2017, A

25
[ 712-50-5 ]
[ 1135-67-7 ]

Reference： [1]Bulletin de la Societe Chimique de France,1964,p. 2908 - 2916

26
[ 712-50-5 ]
[ 947-19-3 ]

Yield	Reaction Conditions	Operation in experiment
90.2%	With tetrabutylammomium bromide; sodium hydroxide; In tetrachloromethane; at 80 - 90℃; for 12h;	n a 1000 ml three-necked flask, 178.7 g of crude cyclohexyl phenyl ketone, 5.36 g of tetrabutylammonium bromide, 220 g of carbon tetrachloride and 76 g of sodium hydroxide were added, and the condenser was connected.The mixture was heated and stirred at 80-90 C for 12 hours. After the reaction was completed, it was cooled to room temperature, diluted with 200 g of dichloromethane, and the organic layer was washed with saturated brine until neutral. The finished photoinitiator 184 was 174.8 g, and the yield was 90.2%
86.62%	With di-tert-butyl peroxide; In dichloromethane; at 50℃;Sonication;	94.14g (0.5mol) of cyclohexyl phenyl ketone, dichloromethane (200ml), 231.15g (5mol) of di-tert-butyl peroxide were uniformly mixed, placed in an ultrasonic rod (80KHz), stirred vigorously, and the reaction was controlled. The temperature is around 50 C,The reaction was carried out and the progress of the reaction was monitored using TLC or GC.After the completion of the reaction, a sodium hydrogen sulfite solution (containing 187.3 g of sodium hydrogen sulfite) was slowly added dropwise to the reaction system to carry out a quenching reaction.Stir until no peroxide is detected with the starch-potassium iodide test paper, then stir for 30 min. Then continue testing with the test paper until there is no peroxide.After standing and layering, the organic layer is washed with water to neutrality, and the dichloromethane is recovered by atmospheric pressure, and the solvent is further recovered by reducing the pressure.When the solvent and the low-boiling substance were removed, the distillation was carried out under reduced pressure, and a fraction of 107-109 C / 1.8 kPa was collected, and the mixture was cooled to a white solid.88.47 g was obtained, the yield was 86.62%, and the GC content was 99.58%.
85%	With dihydrogen peroxide; In dichloromethane; at 30℃;Microwave irradiation;	94.1 g (0.5 mol) of cyclohexyl phenyl ketone, 250 mL of dichloroethane, and 170.0 g (1.5 mol) of 30% hydrogen peroxide solution were uniformly mixed and placed in a microwave reactor (power: 800 W), stirred vigorously, and the reaction temperature was controlled. The reaction was performed at about 30C. The reaction was monitored by TLC or GC. After the reaction was completed, microwave radiation was added to the reaction system to slowly add sodium bisulfite water.The solution (containing 187.3g of sodium bisulfite) was subjected to extraction for 2h, allowed to stand, separated, and the organic phase was washed with water. The solvent was recovered after decompression at atmospheric pressure.Solvents and low-boiling impurities were removed and purified by vacuum distillation to collect 117-119C/0.3mmHg fractions.Colorless oil 1-hydroxycyclohexyl phenyl ketone 86.8g,Place a white solid with a GC content of 99.2% and a yield of 85.0%.It can then be crystallized using petroleum ether to give white crystals.

81.2%		A 500 mL double-walled-jacket multi-necked flask, fitted with a mechanical stirrer, reflux condenser, thermometer and a dropping funnel connected to a thermostat, is charged with 75.3 g (400 mmol) cyclohexyl phenyl ketone, 2.58 g (8 mmol) tetrabutylammonium bromide and 373.3 g (2.80 mol) 30% aqueous sodium hydroxide solution. This is heated with stirring to 82-85 00 and within 90 minutes a solution of 96.6 g (408 mmol)hexachloroethane in 199 g tetrachloroethylene is added. The reaction mixture is stirred for another 3 hours at 84 00. The temperature is then lowered to 60 00 and left unstirred for phase separation. The lower organic phase is split off; the aqueous phase is extracted with 50 g tetrachloroethylene, the organic phases are combined and 100 g water added. pH is then adjusted to 6.0 using 5% acetic acid. The organic phase is splitoff and the product is vacuum distilled.Yield: 66.3 g (81.2%) (1 -hydroxycyclohexyl) phenyl ketone (Irgacure 184) as a pale yellow oil;b.p. 143 00 0.7 mbar, 95% purity (GO). NMR data are identical with the data of anauthentic reference sample.Tetrachloroethylene (b.p. 55 00 200 mbar) is nearly quantitatively recovered (97%, 99.5% purity).
46.5 g	With hydrogen bromide; In dimethyl sulfoxide; at 110℃; for 16h;	47 g (0.25 mol) of cyclohexyl phenyl ketone was dissolved in 282 ml of dimethyl sulfoxide and stirred at room temperature.A mass fraction of 48% hydrobromide 4.2 g (0.025 mol) was added dropwise, and the temperature was raised to 110 C. The reflux reaction was carried out for 16 h.The reaction was confirmed by HPLC, and the content of 1-hydroxycyclohexyl phenyl ketone was 95.2%.The reaction was stopped, and dimethyl sulfoxide was recovered by distillation under reduced pressure to obtain 52.4 g of a brown gum.Distillation under reduced pressure gave 47.3 g of light brown solid, which was again recrystallized to give 46.5 g of a white solid, content of 99.5%.

Reference： [1]Angewandte Chemie - International Edition,2014,vol. 53,p. 548 - 552
Angew. Chem.,2014,vol. 53,p. 558 - 562,5
[2]Patent: CN108911959,2018,A .Location in patent: Paragraph 0031; 0034; 0035; 0038; 0039; 0040; 0043
[3]Patent: CN109694310,2019,A .Location in patent: Paragraph 0032-0035
[4]Patent: CN107739303,2018,A .Location in patent: Paragraph 0016
[5]Patent: WO2018/197325,2018,A1 .Location in patent: Page/Page column 44
[6]Bulletin de la Societe Chimique de France,1964,p. 2908 - 2916
[7]Patent: CN109369406,2019,A .Location in patent: Paragraph 0019; 0020
[8]Inorganic Chemistry,2019,vol. 58,p. 7584 - 7592
[9]Green Chemistry,2019,vol. 21,p. 2952 - 2966

27
[ 712-50-5 ]
[ 1136-58-9 ]

Yield	Reaction Conditions	Operation in experiment
100%	With hydroxylamine hydrochloride
98%	With hydroxylamine hydrochloride; sodium acetate In ethanol; water Reflux;
75%	With hydroxylamine hydrochloride In ethanol; water at 80℃; Reflux;	1.2 Synthesis of the ketoximes General procedure: In a typical procedure, 100 mL of three-neck round-bottom flask was charged with 13 mmol of ketone and 25 mmol of hydroxylamine hydrochloride. The mixture was dissolved in 12 mL ethanol and 5 mL water and refluxed at 80 o C. 3.5 mL of 20% NaOH aqueous solution (21 mmol of base) was then added into the reaction, which was continuingly refluxed for several hours until the ketone consumed completely as indicated by TLC. The warm solution was cooled down and products were obtained by filtration or extraction.

	With hydroxylamine hydrochloride; sodium acetate In methanol at 20℃; for 15h;	18 1-cyclohexyl-4,5,6,7-tetrahydro-1H-indazole-3-carboxylic acid (cyclohexyl-phenyl)methylamide (Cpd 331) Hydroxylamine hydrochloride (0.48 g, 6.7 mMol) and sodium acetate (1.4 g, 10.2 mMol) were added to a round bottom flask containing cyclohexyl-phenyl-methanone Compound 18a (0.97 g, 5.1 mMol) in MeOH (30 mL) at r.t. The mixture was stirred at r.t. for 15 hrs. The solvent was removed in vacuo and the residue was extracted with CH2Cl2. The organic layer was sequentially washed with a saturated solution of NaHCO3, then brine. The organic layer was dried over Na2SO4, decanted and the solvent removed in vacuo to provide cyclohexyl-phenyl-methanone oxime Compound 18b (1.0 g) as a white solid, which was used in the next step without purification. MS m/z 204 (MH+). A solution of Compound 18b (0.45 g, 0.22 mMol) in anhydrous THF (10 mL) added dropwise via syringe to a suspension of LAH (0.5 g, 1.3 mMol) in THF (20 mL) at 0° C. The mixture was heated to reflux for 8 hrs and provided a grayish suspension. The suspension was cooled to 0° C. and the reaction was quenched carefully by sequential addition of water (0.5 mL), 2N NaOH (0.5 mL) and water (1.5 mL). A white residue was produced, then filtered through a sintered glass funnel and washed with Et2O (20 mL). The solvent from the combined filtrate was removed in vacuo to provide C-cyclohexyl-C-phenyl-methylamine Compound 18c (0.38 g, 91%) as a pale yellow oil, which was used in the next step without purification. MS m/z 190 (MH+). Using the procedure of Example 5, Compound 18c was reacted with acid chloride Compound 5e to provide Compound 331.
	With hydroxylamine hydrochloride; sodium acetate In ethanol at 60℃; for 6h;	93 First step, hydroxyamine hydrochloride (2.20 g) and NaOAc (5.23 g) were added to a solution of benzoylcyclohexane (3 g) in EtOH (80 ml). The reaction mixture was stirred at 60°C for 6 h. EtOH was removed under reduced pressure. H2O (40 ml) was added to the residue, and the resulting solution was extracted with EtOAc (3 × 40 ml). The EtOAc of the combined organic layer was removed by rotary evaporation under reduced pressure to yield benzoylcyclohexane oxime (3.25 g) as a pale yellowish solid. Second step, benzoylcyclohexane oxime (3.25 g) and concentrated HCl (8.45 ml) in EtOH (50 ml) was subjected to hydrogenation at atmospheric pressure in the presence of 10% Pd/C (339 mg). The reaction solution was filtered and the filtrate was concentrated. The residue was suspended in EtOAc, and the suspension was filtered to yield 1-(cyclohexylphenyl)-methylamine hydrochloride (3.5 g) as a white solid. Third step, a mixture of 1-(cyclohexylphenyl)-methylamine (474 mg, the hydrochloride), 6-chloropurine riboside (200 mg) and triethylamine (3 ml) in PrOH (60ml) was heated to 70°C and reacted for 8 h. After evaporation of the reaction mixture, the residue was separated by column chromatography over silica gel and eluted with CHCl3-CH3OH (20 : 1) to yield N6-[(+/-)-1-(cyclohexylphenyl)-methyl]-adenosine(245 mg) as a white solid: positive ESIMS m/z 440 [M + H]+, 462 [M + Na]+ and 478 [M + K]+; negative ESIMS m/z 438 [M - H]- and 474 [M + Cl]-; 1H NMR (300 MHz, DMSO-d6): the adenosine moiety δ 8.35 (1H, s, H-2), 8.28 (1H, brd, J = 7.5 Hz, -NH), 8.16 (1H, s, H-8), 5.87 (1H, d, J= 6.0 Hz, H-1), 5.43 (2H, m, 2×-OH), 5.18 (1H, d, J= 4.2 Hz, -OH), 4.59 (1H, m, H-2'), 4.14 (1H, m, H-3'), 3.95 (1H, m, H-4'), 3.66 (1H, m, H-5'a), 3.55 (1H, m, H-5'b); the (+/-)-1-(cyclohexylphenyl)-methyl moiety δ 7.45 (2H, d, 7.8Hz, H-2", H-6"), 7.27 (2H, t, J = 7.8 Hz, H-3", H-5"), 7.17 (1H, t, J = 7.8Hz, H-4"), 5.10 (1H, m, H-7"), 1.99-0.85 (11H, m, H-1~H-6); 13C NMR (75 MHz, DMSO-d6): the adenosine moiety δ 154.4 (s, H-6), 152.3 (d, C-2), 148.4 (s, C-4), 139.8 (d, C-8), 119.7 (s, C-5), 88.1 (d, C-1), 85.9 (d, C-4'), 73.5 (d, C-2'), 70.7 (d, C-3'), 61.7 (t, C-5'); the (+/-)-1-(cyclohexylphenyl)-methyl moiety δ 142.9 (s, C-1), 128.1 (d, C-2", C-6"), 127.7 (d, C-3", C-5"), 126.7 (d, C-4"), 58.8 (d, C-7"), 41.5 (d, C-1), 30.0 (t, C-2, C-6), 26.0 (t, C-4), 25.4 (t, C-3"', C-5)ο
3.25 g	With hydroxylamine hydrochloride; sodium acetate In ethanol at 60℃; for 6h;	93 First step, hydroxyamine hydrochloride (2.20 g) and NaOAc (5.23 g) were added to a solution of benzoylcyclohexane (3 g) in EtOH (80 ml). The reaction mixture was stirred at 60° C. for 6 h. EtOH was removed under reduced pressure. H2O (40 ml) was added to the residue, and the resulting solution was extracted with EtOAc (3*40 ml). The EtOAc of the combined organic layer was removed by rotary evaporation under reduced pressure to yield benzoylcyclohexane oxime (3.25 g) as a pale yellowish solid.
	With hydroxylamine hydrochloride Alkaline conditions;
3.25 g	With hydroxylamine hydrochloride; sodium acetate In ethanol at 60℃; for 6h;	93.1 First step precisely weigh cyclohexyl phenyl ketone (3 g), hydroxylamine hydrochloride (2.20 g) and anhydrous sodium acetate (5.23 g), dissolve in ethanol (80 mL), stir at 60° C. for 6 h, Recove the solvent with the reaction solution, add 40 mL of water, mix thoroughly, dissolve, extract with ethyl acetate 40 ml, extract a total of 3 times, recover the solvent with the ethyl acetate phase, a light yellow solid Of cyclohexyl phenyl ketone oxime (3.25 g).
	With hydroxylamine hydrochloride; sodium acetate In ethanol; water Reflux;

Reference： [1]Tang, Wenjun; Capacci, Andrew; Sarvestani, Max; Wei, Xudong; Yee, Nathan K.; Senanayake, Chris H. [Journal of Organic Chemistry, 2009, vol. 74, # 24, p. 9528 - 9530]
[2]Mo, Xiaobin; Morgan, Timothy D. R.; Ang, Hwee Ting; Hall, Dennis G. [Journal of the American Chemical Society, 2018, vol. 140, # 15, p. 5264 - 5271]
[3]Ma, Ruonan; Chen, Xueyuan; Xiao, Zhiyin; Natarajan, Mookan; Lu, Chunxin; Jiang, Xiujuan; Zhong, Wei; Liu, Xiaoming [Tetrahedron Letters, 2021, vol. 63]
[4]Current Patent Assignee: JOHNSON & JOHNSON INC - US2005/228034, 2005, A1 Location in patent: Page/Page column 118-119
[5]Current Patent Assignee: CHINESE ACADEMY OF MEDICAL SCIENCES - EP2511283, 2012, A1 Location in patent: Page/Page column 89-90
[6]Current Patent Assignee: CHINESE ACADEMY OF MEDICAL SCIENCES - US2013/45942, 2013, A1 Location in patent: Paragraph 0370
[7]Ghabbour, Hazem A.; El-Bendary, Eman R.; El-Ashmawy, Mahmoud B.; El-Kerdawy, Mohamed M. [Molecules, 2014, vol. 19, # 3, p. 3417 - 3435]
[8]Current Patent Assignee: CHINESE ACADEMY OF MEDICAL SCIENCES - JP2015/172077, 2015, A Location in patent: Paragraph 0185
[9]Zhang, Xiao; Rovis, Tomislav [Journal of the American Chemical Society, 2021, vol. 143, # 50, p. 21211 - 21217]

28
[ 3581-89-3 ]
[ 712-50-5 ]
[ 1046818-35-2 ]

Yield	Reaction Conditions	Operation in experiment
85%		Step 1. A solution of <strong>[3581-89-3]5-methylthiazole</strong> (2.5 g, 25.2 mmol) in anhydrous THF (50 mL) was cooled to -78 0C under a N2 atmosphere. n-Butyllithium (11 mL of a 2.5 M solution in hexanes) was added dropwise over 5 minutes. The reaction was stirred for 10 minutes before a solution of cyclohexylphenyl ketone in anhydrous THF (50 mL) was added dropwise. The reaction was stirred for 30 minutes at -78 0C then allowed to warm to ambient temperature before being quenched by addition of sat. Na2CO3 and extracted into diethyl ether. The combined organic extracts were washed with brine, dried (MgSO4) and concentrated. Purification by chromatography using 0-10% EtOAc/heptanes gave cyclohexyl-(5-methyl-thiazol-2-yl)-phenyl-methanol (6.15 g, 85%). 1H NMR (300 MHz,CDCI3): delta 7.6-7.7 (2 H, m), 7.15-7.40 (4 H, m), 3.8 (1 H, s), 2.30-2.40 (4 H, m), 1.6-1.8 (3H, m), 1.35-1.45 (2 H, m), 1.05-1.3 (5 H, m).
85%		A solution of <strong>[3581-89-3]5-methylthiazole</strong> (2.5 g, 25.2 mmol) in 50 mL anhydrous THF was cooled to -78 0C under a N2 atmosphere. n-Butyllithium (11 mL of a 2.5M solution in hexanes) was added dropwise over 5 minutes. The reaction was stirred for 10 minutes before a solution of cyclohexylphenyl ketone in 50 mL anhydrous THF was added dropwise. The reaction was stirred for 30 minutes at -78 0C then allowed to warm to ambient temperature before being quenched by addition of sat. Na2CO3 and extracted into diethyl ether. The combined organic extracts were washed with brine, dried (MgSO4) and concentrated. Purification by chromatography using 0-10% EtOAc/heptanes gave the title compound. Yield: 6.15 g (85%).1H NMR (CDCI3) delta 1.05-1.3 (5 H, m), 1.35-1.45 (2 H, m), 1.6-1.8 (3 H, m), 2.30- 2.40 (4 H, m), 3.8 (1 H, s), 7.15-7.40 (4 H, m), 7.6-7.7 (2 H, m).

Reference： [1]Patent: WO2008/99186,2008,A1 .Location in patent: Page/Page column 63
[2]Patent: WO2008/96093,2008,A1 .Location in patent: Page/Page column 26

29
[ 78-08-0 ]
[ 712-50-5 ]
[ 1151886-44-0 ]

Yield	Reaction Conditions	Operation in experiment
100%	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; sodium formate; triphenylphosphine In toluene at 140℃; for 1h;

Reference： [1]Martinez, Remi; Simon, Marc-Olivier; Chevalier, Reynald; Pautigny, Cyrielle; Genet, Jean-Pierre; Darses, Sylvain [Journal of the American Chemical Society, 2009, vol. 131, p. 7887 - 7895]

30
[ 712-50-5 ]
[ 1779-49-3 ]
[ 5700-44-7 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: triphenylmethylphosphonium bromide With n-butyllithium In diethyl ether; hexane at 0℃; for 1h; Inert atmosphere; Stage #2: Cyclohexyl phenyl ketone In diethyl ether; hexane at 20℃; Inert atmosphere;
89%	Stage #1: triphenylmethylphosphonium bromide With n-butyllithium In tetrahydrofuran; hexanes at 2℃; for 1.25h; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran; hexanes at 2 - 20℃;	11.A Cyclohexylstyrene was prepared from cyclohexyl phenyl ketone using standard Wittig chemistry (Gupta, P.; Fernandes, R. A.; Kumar, P. Tet. Lett. 2003, 44, 4231-4232. ) Methyltriphenylphosphonium bromide (29.57 g, 82.77 mmol) was slurried in 600 mL THF in the glovebox. The mixture was cooled to 2 °C;, and nBuLi (1.6 M in hexanes, 52 mL) was added over 15 min. After 1 h, solid cyclohexyl phenyl ketone (15.18 g, 80.63 mmol) was added, and the solution was allowed to slowly warm to room temperature overnight. Water (200 mL) was added. The solution was extracted with EtzO (3 x 150 mL). The combined organic extracts were washed with brine, dried (MgS04) and evaporated under vacuum to give a tan liquid. Ph3PO crystallized upon standing and was removed by filtration and washed with hexane (200 mL). The hexane solution was filtered through a 2 in column of neutral alumina, washing with an additional 200 mL of hexane. The filtrate was evaporated to a colorless liquid which was distilled (46-49 °C/0. 1 mm Hg) to give 13.72 g of colorless liquid (89% yield).
67%	Stage #1: triphenylmethylphosphonium bromide With sodium hydride In tetrahydrofuran for 1h; Reflux; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran at 0℃; Reflux;

66%	Stage #1: triphenylmethylphosphonium bromide With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 0.5h; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran; hexane at -78 - 20℃; for 16h; Inert atmosphere;
	Stage #1: triphenylmethylphosphonium bromide With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 2h; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran; hexane at 0 - 70℃;
	Stage #1: triphenylmethylphosphonium bromide With potassium-t-butoxide In tetrahydrofuran for 0.333333h; Schlenk technique; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran at 20℃; Schlenk technique;
	Stage #1: triphenylmethylphosphonium bromide With sodium tertiary butoxide In tetrahydrofuran at 0℃; Inert atmosphere; Schlenk technique; Sealed tube; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran at 0 - 20℃; for 17h; Inert atmosphere; Schlenk technique; Sealed tube;
	Stage #1: triphenylmethylphosphonium bromide With potassium-t-butoxide In diethyl ether at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: Cyclohexyl phenyl ketone In diethyl ether at 0 - 20℃; for 15h; Inert atmosphere;
	Stage #1: triphenylmethylphosphonium bromide With n-butyllithium In tetrahydrofuran at 0 - 20℃; for 2h; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran at 0 - 24℃;	2.2 General procedure for the preparation of alkenes General procedure: The solution of PPh3CH3Br (3.57g, 10 mmol) in THF (20 mL) was cooled to 0oC, 2.5M n-BuLi (10 mmol) wasadded dropwise to the reaction system and stirred at room temperature for 2 hours. Then the solution of ketone (5mmol) in THF was added dropwise through syringe at 0oC. The reaction mixture continued stirring at 24oC until completion, quenched with saturated NH4Cl solution (5 mL) and extracted with EtOAc for 3 times. The combinedorganic layer was dried over Na2SO4 and concentrated under reduced pressure after filtration. The residue waspurified by silica gel column chromatograph to afford the alkenes.
	Stage #1: triphenylmethylphosphonium bromide With potassium-t-butoxide In diethyl ether at 20℃; Inert atmosphere; Stage #2: Cyclohexyl phenyl ketone In diethyl ether at 0 - 20℃; Inert atmosphere;
	Stage #1: triphenylmethylphosphonium bromide With potassium-t-butoxide In tetrahydrofuran at 0℃; for 0.5h; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran for 12h;
	Stage #1: triphenylmethylphosphonium bromide With potassium-t-butoxide In tetrahydrofuran at 0 - 20℃; for 1h; Inert atmosphere; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran at 0 - 20℃; Inert atmosphere;
	Stage #1: triphenylmethylphosphonium bromide With potassium-t-butoxide In tetrahydrofuran at 0 - 20℃; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran at 0 - 20℃;	General procedure for the preparation of substituted olefin: General procedure: An oven-dried round-bottom flask was charged with CH3PPh3Br (1.5 equiv.) or CH3CH2PPh3Br (1.5equiv.) and THF (carbonyl substrate concentration = 0.2 M). tBuOK (1.5 equiv.) was added to thesuspension at 0 °C. The resulting mixture was allowed to warm up to room temperature and stirred for 1h. The yellow suspension was cooled to 0 °C again followed by portion-wise addition of the carbonylsubstrate (1 equiv.). Subsequently, the mixture was further stirred at room temperature for 1-12 hours.After the completion of the reaction, the solvent was removed by evaporation, the resulting mixture wasdiluted with water (30 mL) and extract with dichloromethane (3 x 20 mL), and the combined organiclayer was dried with anhydrous Na2SO4. Concentration in vacuo followed by silica gel columnpurification with petroleum ether/ethyl acetate eluent gave the desired product in yields range from 50-95%.
	Stage #1: triphenylmethylphosphonium bromide With potassium-t-butoxide In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;	2.2 One typical example for the preparation of alkenes. General procedure: To a suspension of tBuOK (12 mmol, 1.2 equiv.) in anhydrous THF (20 mL) was added MePPh3Br (12 mmol, 1.2 equiv.) under argon atmosphere. The suspension was stirred at room temperature for 1 h. Then corresponding ketone (10 mmol, 1.0 equiv.) was added and the reaction mixture was stirred at the same temperature for 1 h . Then the mixture was filtered through a short pad of silica gel, which was subsequently washed with ethyl acetate (200 mL). After evaporation of the organic solvent, the residue was purified by silica gel column chromatography to provide alkene 1i (1.31g, 90%).
	Stage #1: triphenylmethylphosphonium bromide With sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran Inert atmosphere; Schlenk technique; Reflux;
	Stage #1: triphenylmethylphosphonium bromide With potassium-t-butoxide In tetrahydrofuran at 0℃; for 0.5h; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran at 0℃;

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[12]Jiang, Yi-Min; Yu, Yi; Wu, Shao-Fen; Yan, Hong; Yuan, Yaofeng; Ye, Ke-Yin [Chemical Communications, 2021, vol. 57, # 87, p. 11481 - 11484]
[13]Yu, Yi; Jiang, Yimin; Wu, Shaofen; Shi, Zhaojiang; Wu, Jinnan; Yuan, Yaofeng; Ye, Keyin [Chinese Chemical Letters, 2022, vol. 33, # 4, p. 2009 - 2014]
[14]Zhao, Bin; Pan, Zichen; Zhu, Anqiao; Yue, Yanni; Ma, Mengtao; Xue, Fei [Tetrahedron, 2022, vol. 106-107]
[15]Le Saux, Emilien; Melchiorre, Paolo; Zanini, Margherita [Journal of the American Chemical Society, 2022, vol. 144, # 3, p. 1113 - 1118]
[16]Guo, Zheng; He, Yu-Peng; Liu, Wei; Xie, Jinglei; Yang, Xiaoyu; Zhang, Dekun [Chinese Journal of Chemistry, 2022]

31
[ 712-50-5 ]
[ 91272-81-0 ]
[ 1204122-74-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	Stage #1: 1-pyrrolidin-1-ylmethyl-1H-[1,2,4]-triazole With n-butyllithium In tetrahydrofuran; hexanes at -78 - 20℃; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran; hexanes at -78 - 20℃; Stage #3: With water In tetrahydrofuran; hexanes at 20℃;	17 Cyclohexyl(phenyl)[1-(pyrrolidin-1-ylmethyl)-1H-1,2,4-triazol-5-yl]methanol Preparation 17 Cyclohexyl(phenyl)[1-(pyrrolidin-1-ylmethyl)-1H-1,2,4-triazol-5-yl]methanol 1-(pyrrolidin-1-ylmethyl)-1H-1,2,4-triazole (Preparation 16, 12.0 g, 78.84 mmol) was dissolved in tetrahydrofuran (120 mL) and the solution cooled to -78° C. n-Butyl lithium (2.5M in hexanes, 34.7 ml, 86.7 mmol) was then added dropwise over 30 mins. After warming to room temperature and stirring for 1 hour the reaction mixture was cooled to -78° C. and a solution of cyclohexyl(phenyl)methanone (16.3 g, 86.7 mmol) in tetrahydrofuran (30 mL) added dropwise. After warming to room temperature over 18 hr, water (100 ml) was added and the solvent removed in vacuo. The residue was partitioned with ethyl acetate (200 ml), the aqueous phase separated and re-extracted with ethyl acetate (2*200 ml). The combined organic layers were dried over magnesium sulphate, filtered and the solvent removed in vacuo to furnish the title compound as a yellow oil, in 100% yield, 27.28 g. 1H NMR (400 MHz, CHLOROFORM-d) δ=1.00-1.94 (m, 14H), 2.49 (m 1H), 2.71 (m, 4H), 5.08 (s, 2H), 7.19 (m, 1H), 7.30 (m, 2H), 7.72 (m, 2H), 8.00 (s, 1H) ppm.

Reference： [1]Current Patent Assignee: PFIZER INC; MERCK & CO INC - US2010/10040, 2010, A1 Location in patent: Page/Page column 19-20

32
[ 7677-24-9 ]
[ 712-50-5 ]
[ 62-53-3 ]
[ 1202243-49-9 ]

Yield	Reaction Conditions	Operation in experiment
87%	With MCM-41 anchored sulfonic acid In ethanol at 20℃; for 3.33333h;	4.4. Typical procedure for the synthesis of α-amino nitriles General procedure: To a mixture of carbonyl compound (2a-o or 2a'-f', 1 mmol), amine (3a-c, 1 mmol), and TMSCN (1.2 mmol, 0.15 mL) was added MCM-41-SO3H (1, 5 mg) in 96% EtOH (1.5 mL) at room temperature. The mixture was stirred for an appropriate time indicated in Table 2 or Table 3. After completion of the reaction, as indicated by TLC, 96% EtOH (5 mL) was added to the reaction mixture. The obtained mixture was directly crystallized or filtered to remove the catalyst 1 from solid and viscous products, respectively. In the case of viscous products, the organic solvent of the filtrate was evaporated under reduced pressure to obtain essentially pure products in most cases. Further purification of the viscous products could be performed by silica gel column chromatography (EtOAc-hexane, 1:10).
65%	With nanoporous silica SBA-15-Ph-Pr supported sulfonic acid at 50℃; for 19h; neat (no solvent);

Reference： [1]Location in patent: experimental part Dekamin, Mohammad G.; Mokhtari, Zahra [Tetrahedron, 2012, vol. 68, # 3, p. 922 - 930]
[2]Karimi, Babak; Zareyee, Daryoush [Journal of Materials Chemistry, 2009, vol. 19, # 45, p. 8665 - 8670]

33
[ 766-05-2 ]
[ 98-80-6 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
89%	With bathophenanthroline; water; copper diacetate; manganese(III) triacetate dihydrate In 1,4-dioxane at 90℃;	General procedure for the synthesis of arylketones General procedure: In a 25mL round bottom flask (oven-dried overnight) was added the phenyl boronic acid (1a, 1.0 mmol) followed by the addition of 1,4-dioxane (6mL). To this solution, manganese (III) acetate. dihydrate (5mol%), Bphen (3e, 10mol%), Cu(OAc)2 (5mol%), nitrile (0.5mmol) and water (0.5mmol) were added sequentially. The reaction was then stirred at room temperature for 10min and slowly brought to 90°C under air. The reaction was allowed to run for overnight at the same temperature. After the completion, the reaction mixture was quenched and extracted with ethyl acetate and water. The organic layer was collected, and the aqueous layer was again extracted with ethyl acetate for three more times. The combined organic layer was further washed with sodium bicarbonate and brine solution. The organic layer was then dried over sodium sulfate, filtered and evaporated using rotavap. The crude compound obtained was further purified using column chromatography (EA:hexane 10:90).
85%	With 1,2-bis(diphenylphosphino)ethane nickel(II) chloride; water; zinc(II) chloride In 1,4-dioxane at 80℃; for 8h; Inert atmosphere;

Reference： [1]Moustafa, Dina; Sweet, Chelsea; Lim, Hyun; Calalpa, Brenda; Kaur, Parminder [Tetrahedron Letters, 2018, vol. 59, # 42, p. 3816 - 3820]
[2]Wong, Ying-Chieh; Parthasarathy, Kanniyappan; Cheng, Chien-Hong [Organic Letters, 2010, vol. 12, # 8, p. 1736 - 1739]

34
[ 202197-57-7 ]
[ 712-50-5 ]
[ 1009621-60-6 ]

Yield	Reaction Conditions	Operation in experiment
44%	Stage #1: 5-[1,3]dioxolan-2-yl-1-methyl-1H-imidazole With n-butyllithium In tetrahydrofuran; hexanes at 0℃; for 0.666667h; Stage #2: Cyclohexyl phenyl ketone In tetrahydrofuran; hexanes at 20℃;	73.b A solution of 5-[1 ,3]dioxolan-2-yl-1-methyl-1 H-imidazole (3.8 g, 0.0246 mol) in THF (125 ml_) was cooled to O0C under nitrogen. n-Butyllithium (2.5 M solution in hexanes, 12.8 ml_, 0.032 mol) was added and the reaction mixture allowed to stir at 00C for 40 minutes. A solution of cyclohexylphenyl ketone (5.55 g, 0.0295 mol) in THF (25 mL) was added and the reaction mixture allowed to warm to room temperature over 4 h, and then stirred overnight. The reaction mixture was quenched with saturated aqueous ammonium chloride solution and extracted with ether. The organic layer was dried (MgSO4), filtered and evaporated in vacuo. Purification by column chromatography eluting with 1 :0-9:1 DCM/MeOH gave the title compound (3.73 g, 44%). LC-MS (Method 5) R, 2.30 m/z 343 [MH]+.

Reference： [1]Current Patent Assignee: ASTRAZENECA PLC; CHARLES RIVER LABORATORIES INTERNATIONAL INC - WO2008/23157, 2008, A1 Location in patent: Page/Page column 139

35
[ 626-62-0 ]
[ 1033260-22-8 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
71%	Stage #1: Cyclohexyl iodide; O-(triphenylsilyl)benzaldoxime With triethyl borane In hexane; toluene at 90℃; for 5h; Air atmosphere; Stage #2: With water; sodium hydrogencarbonate In hexane; toluene	Typical procedure for ketone synthesis General procedure: To a stirred solution of O-triphenylsilyl oxime (0.25 mmol) and t-butyl iodide (368 mg, 2.0 mmol) in toluene at 90 °C was added triethyl borane (1.25 mL, 1.0 M solution in hexane, 1.25 mmol) under air atmosphere. The resulting mixture was stirred until the starting material was consumed. The reaction mixture was washed with saturated sodium bicarbonate solution, and the product was extracted into ethyl acetate. The organic layer was dried over MgSO4 and was evaporated under reduced pressure to afford a residue, which was purified by silica gel column chromatography.

Reference： [1]Location in patent: experimental part Kim, Joong-Gon; Mishra, Mithilesh Kumar; Jang, Doo Ok [Tetrahedron Letters, 2012, vol. 53, # 27, p. 3527 - 3529]

36
[ 712-50-5 ]
[ 28047-23-6 ]

Yield	Reaction Conditions	Operation in experiment
71%	With chloro-trimethyl-silane; trimethylsilan In ethyl acetate at 20℃; for 2h;
	Multi-step reaction with 2 steps 1: ethanol; sodium tetrahydroborate / 0 - 20 °C 2: dichloromethane / 20 °C
	Stage #1: Cyclohexyl phenyl ketone With iron(III) chloride In ethyl acetate at 20℃; for 0.0166667h; Stage #2: With dimethylmonochlorosilane In ethyl acetate at 20℃;	General procedure for the deoxygenative chlorination of carbonyl compounds with HMe2SiCl General procedure: A 50 mL single-neck round-bottom flask was loaded with carbonyl compound (10.0 mmol), FeCl3 (0.0811 g, 0.5 mmol),and EtOAc (20 mL). The reaction mixture was stirred at room temperature for 1 min, and then HMe2SiCl (1.4193 g,15.0 mmol) was added. Subsequently, the reaction flask was equipped with a 90° glass joint with a balloon to protect the mixture from moisture. The reaction mixture was stirred vigorously at room temperature until the reaction was completed (as detected by thin-layer chromatography(TLC)). The solution was washed with saturated NaHCO3 solution (3 × 10 mL) to remove FeCl3. The organic layer was dried over anhydrous Na2SO4. The solvent was then removed under vacuum, and the mixture was purified via column chromatography to afford the product.

Reference： [1]Savela, Risto; Wärnå, Johan; Murzin, Dmitry Yu.; Leino, Reko [Catalysis science and technology, 2015, vol. 5, # 4, p. 2406 - 2417]
[2]Current Patent Assignee: ASKA PHARMACEUTICAL CO., LTD. - US2013/85127, 2013, A1
[3]Xing, Bing-Han; Zhao, Xuan-Xuan; Qin, Yu-Jun; Zhang, Pu; Guo, Zhi-Xin [Journal of Chemical Research, 2020, vol. 44, # 11-12, p. 667 - 675]

37
[ 611-99-4 ]
[ 712-50-5 ]
1,1-bis(4-hydroxyphenyl)-2-cyclohexyl-2-phenylethene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With titanium tetrachloride; zinc In tetrahydrofuran at 0 - 90℃; for 5h; Inert atmosphere; Darkness;	1,1-Bis(4-hydroxyphenyl)-2-cyclohexyl-2-phenylethene To a suspension of zinc powder (1.15 g, 17.6 mmol) in THF (8 mL) at -10 °C was added titanium(IV) chloride (d 1.726, 0.872 mL, 7.93 mmol). The reaction mixture was diluted with THF (6 mL) and refluxed at 90 °C (bath temperature) for 2 h and then a mixture of 4,4’-dihydroxybenzophenone (891 mg, 4.16 mmol) and cyclohexyl phenyl ketone (245 mg, 1.30 mmol) in THF (15 mL) was added to the mixture at 0 °C. After the reaction mixture had been refluxed at 90 °C (bath temperature) for 5 h in the dark, 10% aqueous potassium carbonate was added to the mixture at 0 °C in the light. The mixture was filtered through a short pad of Celite with ethyl acetate, and the filtrate was extracted with ethyl acetate. The organic layer was washed with brine, and dried over sodium sulfate. After filtration of the mixture and evaporation of the solvent, the crude product was purified by column chromatography on silica (eluant; hexane/ethyl acetate= 2/1) to afford 1,1-bis(4-hydroxyphenyl)-2-cyclohexyl-2-phenylethene (314 mg, 65%) as a white solid

Reference： [1]Hasegawa, Makoto; Yasuda, Yukari; Tanaka, Makoto; Nakata, Kenya; Umeda, Eri; Wang, Yanwen; Watanabe, Chihiro; Uetake, Shoko; Kunoh, Tatsuki; Shionyu, Masafumi; Sasaki, Ryuzo; Shiina, Isamu; Mizukami, Tamio [European Journal of Medicinal Chemistry, 2014, vol. 71, p. 290 - 305]

38
[ 712-50-5 ]
[ 1759-68-8 ]
[ 2719-26-8 ]

Yield	Reaction Conditions	Operation in experiment
62%	With mesitylenesulfonylhydroxylamine; In acetonitrile; at 20℃; for 7h;	General procedure: To a round bottom flask, equipped with a magnetic stirring bar, was added ketone 1 (0.5 mmol, 1.0 equiv.) and acetonitrile (2 mL) at room temperature. To this stirred solution, freshly prepared O-(Mesitylsulfonyl)hydroxylamine 2 (2.0 equiv.) was added. The reaction mixture was stirred for the specified duration and temperature. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with ethyl acetate (10 mL) and washed with a saturated aqueous NaHCO3 solution (3 x 5 mL). The combined organic layer was washed with brine solution and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure to get the crude product. The reaction that required elevated temperature was stirred first at room temperature for 2 hours after addition of MSH and then heated at 70 C for the specified time.

Reference： [1]Tetrahedron Letters,2020,vol. 61
[2]Journal of the Iranian Chemical Society,2014,vol. 11,p. 1287 - 1294
[3]Journal of the American Chemical Society,2018,vol. 140,p. 5264 - 5271
[4]Journal of the American Chemical Society,2021,vol. 143,p. 21211 - 21217

39
[ 5700-44-7 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
92%	With trimethylsilylazide; tetrabutylammonium tetrafluoroborate; oxygen In methanol at 10℃; for 2h; Electrochemical reaction;
73%	With iron(III) trifluoromethanesulfonate; C₆₅H₇₇N₅O₄S₂; oxygen In 1,2-dichloro-ethane at 75℃; for 8h; Green chemistry; chemoselective reaction;
69%	With tert.-butylhydroperoxide; dirhodium (II) tetracaprolactamate In cyclohexane; water at 80℃; for 18h; Sonication; Sealed tube;

62%	With dibenzyl diselenide; dihydrogen peroxide In ethanol; water at 120℃; for 48h; Sealed tube; Green chemistry;
31%	With di-tert-butyl peroxide; iron(II) chloride In decane; acetonitrile at 20℃; for 8h; Inert atmosphere; Schlenk technique;

Reference： [1]Jiang, Haobin; Wang, Feng; Ye, Zenghui; Zhang, Fengzhi; Zhu, Rongjin [Organic Letters, 2021, vol. 23, # 21, p. 8240 - 8245]
[2]Gonzalez-De-Castro, Angela; Xiao, Jianliang [Journal of the American Chemical Society, 2015, vol. 137, # 25, p. 8206 - 8218]
[3]Su, Yong-Liang; De Angelis, Luca; Tram, Linh; Yu, Yang; Doyle, Michael P. [Journal of Organic Chemistry, 2020, vol. 85, # 5, p. 3728 - 3741]
[4]Wang, Tingting; Jing, Xiaobi; Chen, Chao; Yu, Lei [Journal of Organic Chemistry, 2017, vol. 82, # 18, p. 9342 - 9349]
[5]Huang, Zhiliang; Qi, Xiaotian; Lee, Jyh-Fu; Lei, Aiwen [Organometallics, 2018, vol. 37, # 10, p. 1635 - 1640]

40
N-(3,5-bis(trifluoromethyl)phenyl)-N-tosylcyclohexanecarboxamide [ No CAS ]
[ 143-66-8 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
83%	With (bis(tricyclohexyl)phosphine)palladium(II) dichloride; potassium carbonate; tricyclohexylphosphine In 1,4-dioxane at 110℃; for 10h; Inert atmosphere; Schlenk technique;	4.4. Typical procedure for acylative Suzuki coupling reaction of amides with sodium tetraarylborates General procedure: Under a N2 atmosphere, to a 10 mL dry flask were added amide (0.5 mmol), sodium tetraarylborate (0.19 mmol), Pd(PCy3)2Cl2(5 mmol%), PCy3 (3 mmol%), K2CO3 (1 mmol), and dry dioxane (4 mL). The mixture was stirred at 110 °C for a given time or monitored by TLC until the starting material was completely consumed. The reaction mixture was diluted with CH2Cl2 (15 mL), followed by washing with H2O (2 10 mL). The organic layer was dried over Na2SO4, filtered, and evaporated under reduced pressure to give crude product, which was purified by column chromatography on silica gel to afford product.

Reference： [1]Li, Xijing; Zou, Gang [Journal of Organometallic Chemistry, 2015, vol. 794, p. 136 - 145]

41
[ 712-50-5 ]
[ 56-81-5 ]
(2-cyclohexyl-2-phenyl-[1,3]-dioxolan-4-yl)methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With toluene-4-sulfonic acid In toluene Reflux;	1 (2-Cyclohexyl-2-phenyl- [1,3]-dioxolan-4-yl)methanol (2) An excess of glycerol (26.56 mmol) and a catalytic amount of p-toluenesulfonic acid (0.53 mmol) were added to a solution of cylohexylphenyl ketones (13.28 mmol) in toluene (250 mL). The mixture was refluxed and water was removed in a Dean-Stark trap until the formation of water stopped. After completion of the reaction a mixture of CH2Cl2/H2O was added. The organic layer was separated and the aqueous layer was extracted with CH2Cl2. The organic layers were combined, washed with a saturated solution of NaHCO3 and brine, dried over anhydrous Na2SO4, filtered and concentrated under vacuum. The unassigned diastereoisomeric mixture of the title compound was obtained as a yellow oil (3.31 g, 12.61 mmol, 95% yield) and used without further purification. 1H NMR (DMSO, 200 MHz): δ = 0.91-1.22 (5H, m, Cyc), 1.49-1.72 (7H, m, Cyc, OH), 3.58 (1H, dd, J = 7.2, 8.9 Hz, CHa-5 Diox), 3.76 (1H, dd, J = 7.2, 8.2 Hz, CHb-5 Diox), 4.00 (2H, m, CH2OH), 4.21-4.35 (1H, m, CH-4 Diox), 7.21-7.40 (5H, m, Ar). ESI-HRMS calcd for C16H23O3 [M+H]+ 263.1642, found 263.1645.

Reference： [1]Franchini, Silvia; Battisti, Umberto Maria; Prandi, Adolfo; Tait, Annalisa; Borsari, Chiara; Cichero, Elena; Fossa, Paola; Cilia, Antonio; Prezzavento, Orazio; Ronsisvalle, Simone; Aricò, Giuseppina; Parenti, Carmela; Brasili, Livio [European Journal of Medicinal Chemistry, 2016, vol. 112, p. 1 - 19]

42
C₁₅H₁₅NO₃S*C₇H₈O₂S [ No CAS ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
78%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; 1,3-bis(2,6-diisopropylphenyl)dihydroimidazol-2-ylidene In tetrahydrofuran at 23℃; for 24h;

Reference： [1]Simmons, Bryan J.; Weires, Nicholas A.; Dander, Jacob E.; Garg, Neil K. [ACS Catalysis, 2016, vol. 6, # 5, p. 3176 - 3179]

43
[ 712-50-5 ]
[ 75-24-1 ]
[ 2936-55-2 ]
cyclohexyl(2,6-dimethylphenyl)methanone [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2016,vol. 138,p. 10132 - 10135

44
[ 98-88-4 ]
[ 446065-11-8 ]
[ 712-50-5 ]

Reference： [1]Journal of Organic Chemistry,2017,vol. 82,p. 1856 - 1863

45
[ 4352-39-0 ]
[ 712-50-5 ]
[ 98-86-2 ]

Yield	Reaction Conditions	Operation in experiment
1: 38.7% 2: 60.3%	With ammonium cerium (IV) nitrate; oxygen; trifluoroacetic acid In 1,4-dioxane at 80℃; for 24h;	7.9 Example 1 General procedure: At 1 atm pure oxygen, Add 0.5 mmol to a 10 mL tube1,1-diphenylethanol,Accounting for the molar amount of 1,1-diphenylethanol5% of CAN (cerium ammonium nitrate) and 26.9 mol% of TFA, 2 mL of 1,4-dioxane solvent,Heated to 80 ° C,The reaction was monitored by thin layer chromatography (developing solvent: petroleum ether / ethyl acetate 10: 1).After 24 hours of reaction, the reaction solution was poured into 10mL saturated aqueous ammonium chloride solution, extracted with ether (10 mL, 3 times). The combined organic layers were dried over anhydrous sodium sulfate and evaporated to drynessThe residue was separated by column chromatography (eluent: petroleum ether / ethyl acetate 10: 1). The product was benzophenone in a yield of 90.8%.

Reference： [1]Current Patent Assignee: YANGZHOU UNIVERSITY - CN105152829, 2017, B Location in patent: Paragraph 0015; 0016; 0017; 0018; 0019; 0020; 0021-0047

46
[ 108-86-1 ]
[ 2043-61-0 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
88%	With palladium diacetate; potassium hydrogencarbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In acetone at 20℃; for 48h; Irradiation; Inert atmosphere;	1; 10-12; 4-5; 9-10; 11 Example 1 Reaction conditions: Bromobenzene (0.4mmol), cyclohexanecarbaldehyde (0.6mmol), TBADT (2mol%, 0.008mmol), Pd(OAc)2(5mol%), 0.02mmol), Xantphos is 4,5-bis(diphenyl) Phosphine)-9,9-dimethylxanthene (5mol%, 0.02mmol), potassium bicarbonate (110mol%, 0.44mmol) and acetone (5.0ml). In a PhotoRedOx Box equipped with a fan, the mixture was irradiated for 48h with a 34W390 nm Kessil lamp (Kessil LED photocatalytic lamp PR160) at room temperature under an Ar atmosphere. The mixture was then quenched with saturated NaCl solution (10 mL) and extracted with ethyl acetate (3×10 mL). The organic layers were combined, washed with brine (1×30 mL), and concentrated under vacuum. The product was purified by flash column chromatography on silica gel with hexane/ethyl acetate to obtain the product cyclohexyl (phenyl) ketone as a colorless liquid, and the product yield was 88%.
87%	With palladium diacetate; 9,10-phenanthrenequinone; potassium hydrogencarbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In acetone at 20℃; for 24h; Irradiation;
28%	With palladium diacetate; N-cyclohexylpyridine-2-carboxamide; potassium hydrogencarbonate In tert-Amyl alcohol at 150℃; for 24h;

90 %Spectr.

With palladium diacetate; 9,10-phenanthrenequinone; potassium hydrogencarbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In acetone at 20℃; for 24h; Inert atmosphere; Irradiation;

1-14 Example 1 Reaction conditions: bromobenzene (0.4mmol), cyclohexanecarboxaldehyde (0.6mmol), AQ (10mol%, 0.04mmol), Pd(OAc)2 (5mol%), 0.02mmol), Xantphos is 4,5-bis (Diphenylphosphine)-9,9-dimethylxanthene (5mol%, 0.02mmol), potassium bicarbonate (110mol%, 0.44mmol) and acetone (5.0ml). In a PhotoRedOx Box equipped with a fan, the mixture was irradiated with a 427nm Kessil lamp (Kessil LED photocatalytic lamp PR160) at room temperature and Ar atmosphere for 24h. The mixture was then quenched with saturated NaCl solution (10 mL) and extracted with ethyl acetate (3×10 mL). The organic layers were combined, washed with brine (1×30 mL), and concentrated under vacuum. The product was purified by flash column chromatography on silica gel with hexane/ethyl acetate to obtain the pure product cyclohexyl (phenyl) ketone as a colorless liquid. Using diphenylmethane as an internal standard, the yield was determined by 1H-NMR, and the product yield was 90%.

Reference： [1]Current Patent Assignee: HAINAN NORMAL UNIVERSITY - CN111646875, 2020, A Location in patent: Paragraph 0040-0044; 0107-0112; 0119-0122; 0129-0134
[2]Chen, Guangying; Cheng, Gui-Juan; Guo, Bin; Li, Xiaobao; Ran, Chongzhao; Wang, Lu; Wang, Ting; Wei, Jun-Jie; Zheng, Caijuan; Zheng, Chao [ACS Catalysis, 2020, vol. 10, # 14, p. 7543 - 7551]
[3]Wakaki, Takayuki; Togo, Takaya; Yoshidome, Daisuke; Kuninobu, Yoichiro; Kanai, Motomu [ACS Catalysis, 2018, vol. 8, # 4, p. 3123 - 3128]
[4]Current Patent Assignee: HAINAN NORMAL UNIVERSITY - CN111620768, 2020, A Location in patent: Paragraph 0039-0043; 0107-0124

47
[ 667-27-6 ]
[ 712-50-5 ]
ethyl 2-(4-(cyclohexanecarbonyl)phenyl)-2,2-difluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With (bis(tricyclohexyl)phosphine)palladium(II) dichloride; iron(II) acetate; potassium carbonate In 1,2-dichloro-ethane at 110℃; for 48h; Schlenk technique; Inert atmosphere; Sealed tube;
74.1%	With rhodamine 6G; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl-formamide at 50℃; for 15h; Irradiation;	8 Example 8 ethyl 2- (4- (cyclohexanecarbonyl) phenyl) -2,2-difluoroacetate (I-h) In a 50 mL round bottom flask equipped with a magnetic stirrer, add compound (II) cyclohexyl (phenyl) ketone (75 mg, 0.4 mmol), rhodamine 6G (19.2 mg, 0.04 mmol), 4,4'-di-tert Butyl-2,2'-dipyridine (53.6 mg, 0.2 mmol), cesium carbonate (521 mg, 1.6 mmol) and ethyl monobromodifluoroacetate (242.4 mg, 1.2 mmol), DMF (5 mL) was added to the mixture The mixture was irradiated with 3W blue light, and the reaction was stirred at 50 ° C for 15 hours, and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layer was dried over anhydrous Mg2SO4 and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane / ethyl acetate to obtain 92 mg of the product, the yield was 74.1%, and the HPLC purity was 98.3%.
71%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium acetate; silver fluoride; triphenylphosphine In hexane at 140℃; for 20h; Sealed tube; Inert atmosphere;	22.1-22.3 In this embodiment, the preparation method of a benzoyl para-difluoroalkylated derivative is as follows: a cyclohexyl phenyl ketone is used as a raw material, and the reaction formula is as follows: (1) Add 0.0593 g (0.2 mmol) of cyclohexyl phenyl ketone to the reaction tube, tetratriphenylphosphine palladium 0.0116 g(0.01 mmol), potassium acetate 0.0786 g (0.8 mmol), triphenylphosphine 0.0157 g (0.06 mmol), silver fluoride 0.0077 g (0.06 mmol), ethyl bromodifluoroacetate 0.0203 g (1.00 mmol) and 0.25 mL Hexane, protected by argon, and reacted at 140 ° C for 20 hours;(2) TLC tracks the reaction until it is completely over;(3) The crude product obtained after the completion of the reaction was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain a target.Product (yield 71%).

71%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium acetate; silver fluoride; triphenylphosphine In hexane at 140℃; for 20h; Inert atmosphere; Sealed tube;
50%	With tris[2-phenylpyridinato-C₂,N]iridium(III); 1,10-Phenanthroline; sodium acetate In acetonitrile at 20℃; for 24h; Schlenk technique; Inert atmosphere; Irradiation;

Reference： [1]Mao, Yang-Jie; Wang, Bing-Xin; Wu, Qiu-Zi; Zhou, Kun; Lou, Shao-Jie; Xu, Dan-Qian [Chemical Communications, 2019, vol. 55, # 14, p. 2019 - 2022]
[2]Current Patent Assignee: ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN111018708, 2020, A Location in patent: Paragraph 0027
[3]Current Patent Assignee: SOOCHOW UNIVERSITY (SUZHOU) - CN108586251, 2018, A Location in patent: Paragraph 0177-0182
[4]Tu, Guangliang; Yuan, Chunchen; Li, Yuting; Zhang, Jingyu; Zhao, Yingsheng [Angewandte Chemie - International Edition, 2018, vol. 57, # 47, p. 15597 - 15601][Angew. Chem., 2018, vol. 130, # 47, p. 15823 - 15827,5]
[5]Zhou, Jiadi; Wang, Fang; Lin, Zhihao; Cheng, Cheng; Zhang, Qiwei; Li, Jianjun [Organic Letters, 2020, vol. 22, # 1, p. 68 - 72]

48
[ 712-50-5 ]
[ 2719-26-8 ]

Yield	Reaction Conditions	Operation in experiment
77%	With ethyl O-(methanesulfonyl)acetohydroxamate; toluene-4-sulfonic acid In water; acetonitrile at -10℃; for 24h; Inert atmosphere; chemoselective reaction;
76%	With zinc(II) chloride; hydroxylamine-O-sulfonic acid In water at 20℃; for 16h;	Secondary Amides from Ketones; General Procedure General procedure: To a stirring solution of ZnCl2 (0.05 mmol, 10 mol%) in H2O (2 mL) at r.t. in an open round-bottom flask, ketone 1 (0.5 mmol, 1.0 equiv) wasadded, followed by HOSA (1.5 equiv). The reaction mixture was stirred at the indicated temperature and for the duration indicated in Scheme 2. After completion, the reaction mixture was diluted with EtOAc (15 mL) and washed with sat. aq Na2CO3 (3 × 5 mL). The organic layer was washed with brine (5 mL) and dried over anhydrous Na2SO4.The crude product obtained after removal of all volatiles in vacuo was washed with n-hexane to remove some minor nonpolar impurities.
	Multi-step reaction with 2 steps 1: hydroxylamine hydrochloride / ethanol; water / 80 °C / Reflux 2: 1,3,5-trichloro-2,4,6-triazine / dimethyl sulfoxide; acetonitrile / 5 h / 0 °C

Reference： [1]Hyodo, Kengo; Hasegawa, Genna; Oishi, Naoki; Kuroda, Kazuma; Uchida, Kingo [Journal of Organic Chemistry, 2018, vol. 83, # 21, p. 13080 - 13087]
[2]Verma, Saumya; Kumar, Puneet; Khatana, Anil K.; Chandra, Dinesh; Yadav, Ajay K.; Tiwari, Bhoopendra; Jat, Jawahar L. [Synthesis, 2020, vol. 52, # 21, p. 3272 - 3276]
[3]Ma, Ruonan; Chen, Xueyuan; Xiao, Zhiyin; Natarajan, Mookan; Lu, Chunxin; Jiang, Xiujuan; Zhong, Wei; Liu, Xiaoming [Tetrahedron Letters, 2021, vol. 63]

49
pentafluorophenyl cyclohexanecarboxylate [ No CAS ]
[ 98-80-6 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
79%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium carbonate; tricyclohexylphosphine tetrafluoroborate In 1,4-dioxane at 120℃; for 15h; Inert atmosphere; Schlenk technique;	General Procedure for Cross-Coupling of Pentafluorophenyl Esters General procedure: An oven-dried vialequipped with a stir bar was charged with an ester substrate (neat, 1.0 equiv), boronic acid(typically, 3.0 equiv), sodium carbonate (typically, 4.5 equiv), Pd2(dba)3 (typically, 3 mol%), andPCy3HBF4 (typically, 12 mol%), placed under a positive pressure of argon, and subjected tothree evacuation/backfilling cycles under high vacuum. Dioxane (typically, 0.25 M) was addedwith vigorous stirring at room temperature, the reaction mixture was placed in a preheated oilbath at 120 °C, and stirred for the indicated time at 120 °C. After the indicated time, the reactionmixture was cooled down to room temperature, diluted with CH2Cl2 (10 mL), filtered, andconcentrated. The sample was analyzed by 1H NMR (CDCl3, 500 MHz) and GC-MS to obtainconversion, selectivity and yield using internal standard and comparison with authentic samples.Purification by chromatography afforded the pure product.

Reference： [1]Buchspies, Jonathan; Pyle, Daniel J.; He, Huixin; Szostak, Michal [Molecules, 2018, vol. 23, # 12]

50
[ 17763-67-6 ]
[ 100-49-2 ]
[ 712-50-5 ]

Reference： [1]Journal of the American Chemical Society,2019

51
[ 947-19-3 ]
[ 712-50-5 ]

Reference： [1]Chemical Science,2019,vol. 10,p. 9345 - 9350

52
[ 67-56-1 ]
[ 2446-83-5 ]
[ 712-50-5 ]
[ 93-58-3 ]
[ 1433188-00-1 ]

Yield	Reaction Conditions	Operation in experiment
1: 79 %Chromat. 2: 75%	Stage #1: di-isopropyl azodicarboxylate; Cyclohexyl phenyl ketone With cerium(IV) trifluoromethanesulfonate; trimethylsilyl cyanide; 9,10-diphenylanthracene; tetrabutyl-ammonium chloride; titanium tetrachloride In acetonitrile at 0 - 50℃; for 24h; Inert atmosphere; Irradiation; Glovebox; Stage #2: methanol With triethylamine In acetonitrile at 20℃; for 2h; Inert atmosphere; Glovebox;	4.3 General procedure for selective C-C bond cleavage of medium-size cyclicand linear ketones: General procedure: A 8-mL vial was charged with 2-phenylcyclohexanone (35 mg, 0.2 mmol, 1.0equiv.), DIAD (48 μL, 0.24 mmol, 1.2 equiv.), DPA (3.3 mg, 10 μmol, 0.05 equiv.),Ce(OTf)4 (2.9 mg, 4 μmol, 0.02 equiv.), n-Bu4NCl (5.5 mg, 20 μmol, 0.1 equiv.) inglovebox, then the vial was sealed with a poly-tetrafluoroethylene-lined cap before CH3CN (1 mL), PhCF3 (1 mL) was added. TiCl4 (0.1 mL, 0.2 M in CH3CN, 0.1 equiv.)and TMSCN (76 μL, 0.6 mmol, 3 equiv.) was added at 0 °C. The reaction mixture wasdegassed by Argon sparging for 2 min at 0 °C, then irradiated with a 100 W blue LEDlamp (at approximately 4 cm away from the light source, light intensity 0.16 Wcm-2,the reaction temperature was measured to be 50 °C). After the ketone was consumed,the reaction mixture was cooled to room temperature before anhydrous methanol (4mL) and Et3N (42 μL, 0.3 mmol, 1.5 equiv.) was added. The solution was stirred foranother 2h before concentrated in vacuo. Purification by flash chromatography onsilica gel (20% acetone in hexanes) provided the desired product.

Reference： [1]Chen, Yilin; Du, Jianbo; Zuo, Zhiwei [Chem, 2020, vol. 6, # 1, p. 266 - 279]

53
[ 611-73-4 ]
[ 2043-61-0 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
68%	With dipotassium peroxodisulfate; iron(III)-acetylacetonate; di-tert-butyl peroxide In ethyl acetate at 120℃; for 2h; Sealed tube;
68%	With dipotassium peroxodisulfate; iron(III)-acetylacetonate; di-tert-butyl peroxide In ethyl acetate at 120℃; for 12h;	7 Example 7 The benzoyl formic acid (30.0mg, 0.2mmol), Fe(acac)3 (21.2mg, 0.06mmol),Cyclohexyl formaldehyde (112.0 mg, 1.0 mmol), DTBP (58.5 mg, 0.4 mmol), K2S2O8 (81.1 mg, 0.3 mmol) and a stirring rod were placed in the reaction tube, and 1 mL of ethyl acetate was added as a solvent.Close the reaction tube. Place the reaction tube in an oil bath at 120 ° C, start stirring, and perform constant temperature reaction for 12 hours.After cooling the reaction mixture to room temperature,The solid residue was filtered through a short silica gel column,And washed with 10mL ethyl acetate. After evaporating the solvent in vacuum,The crude product was purified by column chromatography with petroleum ether: ethyl acetate = 50: 1 as eluent to obtain pure product. Colorless liquid, yield 68%.

Reference： [1]Zhou, Fangyuan; Li, Lesong; Lin, Kao; Zhang, Feng; Deng, Guo-Jun; Gong, Hang [Chemistry - A European Journal, 2020, vol. 26, # 19, p. 4246 - 4250]
[2]Current Patent Assignee: XIANGTAN UNIVERSITY - CN111056890, 2020, A Location in patent: Paragraph 0041-0042

54
[ 712-50-5 ]
ethyl 3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butanoate [ No CAS ]
5-cyclohexyl-4-methyl-4,5-diphenyldihydrofuran-2(3H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With potassium hexamethylsilazane In tetrahydrofuran at 100℃; for 3h; Inert atmosphere; Schlenk technique;	Procedure for Lewis Base-Catalyzed Tertiary and Secondary Alkylations of Aldehydes andKetones General procedure: β-Borylacrylate 1a (63.6 mg, 0.2 mmol) wasplaced in a schlenk tube containing a magnetic stirring bar. The tube was sealed with a rubber septum,and then evacuated and filled with nitrogen. THF (1.0 mL), KHMDS (8.0 mg, 0.04 mmol) andbenzaldehyde (2a) were sequentially added to the tube. After 3 h stirring at 80 C, the reaction mixturewas diluted with ethyl acetate (1 mL) then filtered through a short plug of silica gel with ethyl acetateas an eluent. After volatiles were removed under reduced pressure, flash column chromatography onsilica gel (100:0-90:10, hexane/EtOAc) gave 3aa (44.3 mg, 0.175 mmol) in 88% yield.

Reference： [1]Nagao, Kazunori; Nakamura, Kei; Ohmiya, Hirohisa; Sato, Yukiya; Yabushita, Kenya [Bulletin of the Chemical Society of Japan, 2020, vol. 93, # 9, p. 1065 - 1069]

55
[ 108-86-1 ]
[ 766-05-2 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
98%	Stage #1: bromobenzene; cyclohexane carbonitrile With iodine; magnesium In tetrahydrofuran at 80 - 85℃; Stage #2: With sulfuric acid In water at 20 - 25℃; for 2h;	2 Example 2 Add 5.3g magnesium powder to the reactor with condenser,70ml tetrahydrofuran and catalytic amount of iodine, heated to 85°C and refluxed, 35g bromobenzene was added dropwise,Trigger. After the Grignard reagent is made, 20g cyclohexylcarbonitrile dissolved in 20ml tetrahydrofuran is added dropwise,After the dropwise addition is completed, continue to reflux at 80°C for 30 to 60 minutes until the liquid phase detection reaction is completed.Cool to 25°C, then add a mixture of 25ml concentrated sulfuric acid and 50ml water. Stir at room temperature for 2h,The liquid was separated and evaporated to dryness under reduced pressure to obtain 33.8 g of cyclohexyl benzophenone, the yield was 98%, and the liquid phase purity was 96%+.

Reference： [1]Current Patent Assignee: UNIVERSITY OF SCIENCE AND TECHNOLOGY LIAONING - CN111960934, 2020, A Location in patent: Paragraph 0025

56
[ 591-50-4 ]
[ 766-05-2 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	Stage #1: iodobenzene; cyclohexane carbonitrile With iodine; magnesium In tetrahydrofuran at 83 - 85℃; Stage #2: With sulfuric acid In water at 20 - 25℃; for 2h;	3 Example 3 Add 5.3g magnesium powder to the reactor with condenser,70ml of tetrahydrofuran and catalytic amount of iodine, heated to 85°C and refluxed, dripped 45g of iodobenzene,Trigger. After the Grignard reagent is made, 20g cyclohexylcarbonitrile dissolved in 20ml tetrahydrofuran is added dropwise,After the dripping is completed, continue to reflux at 83°C for 30min to 60min until the liquid phase detection reaction is completed.Cool to 25°C, then add a mixture of 28ml concentrated sulfuric acid and 60ml water. Stir at room temperature for 2h,The liquid was separated and evaporated to dryness under reduced pressure to obtain 34.1 g of cyclohexyl benzophenone, with a yield of 99% and a liquid phase purity of 96%+.

Reference： [1]Current Patent Assignee: UNIVERSITY OF SCIENCE AND TECHNOLOGY LIAONING - CN111960934, 2020, A Location in patent: Paragraph 0027

57
[ 766-05-2 ]
[ 108-90-7 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
97%	Stage #1: cyclohexane carbonitrile; chlorobenzene With iodine; magnesium In tetrahydrofuran at 85℃; Stage #2: With sulfuric acid In water at 20 - 25℃; for 2h;	1 Example 1 Add 5.3g magnesium powder to the reactor with condenser,70ml tetrahydrofuran and catalytic amount of iodine, heated to 85°C and refluxed, 25g chlorobenzene was added dropwise,Trigger. After the Grignard reagent is made, 20g cyclohexylcarbonitrile dissolved in 20ml tetrahydrofuran is added dropwise,After the addition is complete, continue refluxing at 85°C for 30min to 60min until the liquid phase detection reaction is complete.Cool to 25°C, then add a mixed acid solution of 22ml concentrated sulfuric acid and 50ml water.Stir at room temperature for 2 hours, separate liquids and evaporate to dryness under reduced pressure to obtain 33.5 g of cyclohexyl phenyl ketone with a yield of 97%.The purity of the liquid phase is 96%+.

Reference： [1]Current Patent Assignee: UNIVERSITY OF SCIENCE AND TECHNOLOGY LIAONING - CN111960934, 2020, A Location in patent: Paragraph 0023

58
1-benzoylcyclohexyl methyl oxalate [ No CAS ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
82%	With 2-(2'-pyridyl)benzimidazole; diphenylsilane; magnesium chloride; nickel dichloride; zinc In N,N-dimethyl acetamide at 40℃; Inert atmosphere; Schlenk technique;	1. General Procedure (GP): General procedure: A flame-dried Schlenk tube was charged with a tertiary alkyl oxalate if it is a solid (0.15 mmol,100 mol%), Zn (24.5 mg, 0.38 mmol, 250 mol%), NiCl2 (1.0 mg, 0.0075 mmol, 5 mol%), MgCl2(28.5 mg, 0.30 mmol, 200 mol%), and PBI (29.3 mg, 0.45 mmol, 100 mol%). The tube was cappedwith a rubber septum. After being evacuated and backfilled with nitrogen three times, diphenylsilane(56.0 μL, 0.30 mmol, 200 mol%) and a tertiary alkyl oxalate if it is a liquid (0.15 mmol, 100 mol%)were added via syringes followed by addition of DMA (2.5 mL), again via a syringe. The reactionmixture was allowed to stir overnight under a N2 atmosphere at 40 C, and was directly loaded onto asilica gel column without work-up. The residue was rinsed with small amount of CH2Cl2 or the eluentand was transferred to a silica gel column. Flash column chromatography offered the product.

Reference： [1]Ye, Yang; Ma, Guobin; Yao, Ken; Gong, Hegui [Synlett, 2021, vol. 32, # 16, p. 1625 - 1628]

59
[ 5700-44-7 ]
[ 75-89-8 ]
[ 75-90-1 ]
[ 712-50-5 ]

Yield	Reaction Conditions	Operation in experiment
95%	With Togni's reagent; C₁₄H₁₆Br₂NO₅V In acetone for 96h;	C-3 General procedure: In a dry double-necked round flask (50 mL), take 5 mol% of the catalyst of formula (II-3) and reagents containing trifluoromethyl or perfluoromethyl (1.5 equivalents) and dissolve them in acetone (1 mL). Next, the unsaturated double bond-containing compound (I-1) (1 equivalent) was added. After the reaction was completed, the solvent was removed in vacuum, and the crude product was purified by silica gel flash column chromatography (ethyl acetate/hexane=1:8) to obtain the product. The results are shown in Table 2.
	With Togni's reagent; oxygen; C₁₄H₁₆Br₂NO₅V In acetone for 96h; Overall yield = 95 percent;	General procedure: In aflame-dried, 25-mL, two-necked, round-bottomed flask was placed 5 mol % catalyst (eq II-3) and trifluoromethyl- or perfluoromethyl-containing reagent (1.5 equiv) dissolved in acetone (I mL). Then, a compound (1-1) (1.0 equiv) with an unsaturated double bond was added. After having the reaction finished, the solvent was removed in vacuo, and the crude product was purified by using flash column chromatography on silica gel (ethyl acetate/hexane=1/8) to afford the product. The result is shown in Table 2.

Reference： [1]- CN113061069, 2021, A Location in patent: Paragraph 0108-0114; 0115-0120; 0185-0187
[2]Current Patent Assignee: TSINGHUA UNIVERSITY (TAIWAN) - US2021/206702, 2021, A1 Location in patent: Paragraph 0071; 0074

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	712-50-5	MDL No. :	MFCD00001467
Formula :	C₁₃H₁₆O	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	BMFYCFSWWDXEPB-UHFFFAOYSA-N
M.W :	188.27 g/mol	Pubchem ID :	12837
Synonyms :

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H315-H319	Packing Group:	N/A
GHS Pictogram:

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

[ CAS No. 712-50-5 ]

Quality Control of [ 712-50-5 ]

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Application In Synthesis of [ 712-50-5 ]

[ 712-50-5 ] Synthesis Path-Upstream 1~1

[ 712-50-5 ] Synthesis Path-Downstream 1~59

Related Functional Groups of
[ 712-50-5 ]

Aryls

Ketones

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