Name: 585-74-0|1-(m-Tolyl)ethanone|98%
Brand: Ambeed
SKU: A182131
Price: 19.0 USD
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1
[ 7287-81-2 ]
[ 585-74-0 ]

Yield	Reaction Conditions	Operation in experiment
99%	With [(2-(benzoimidazol-2-yl)-6-(3,5-dimethylpyrazol-1-yl)pyridine)RuCl2(PPh3)]; potassium tert-butylate; acetone; In methanol; at 56℃; under 750.075 Torr; for 0.0833333h;Inert atmosphere;Catalytic behavior;	General procedure: The catalyst solutionwas prepared by dissolving complex 3(36.1 mg,0.05mmol) in methanol (5.0 mL).Under a nitrogen atmosphere, the mixture of an alcohol substrate (2.0 mmol) and1.0 mL of the catalyst solution (0.01mmol) in 20mL acetone was stirred at 56 Cfor 10 minutes. tBuOK(22.4mg, 0.2 mmol)was then added to initiate the reaction.At the stated time, 0.1 mL of the reaction mixture was sampled and immediately diluted with 0.5 mL acetone pre-cooled-to-0 C for GC or NMR analysis. After the reaction was complete, the reaction mixture was condensed under reduced pressure and subject to purification by flash silica gel column chromatography to afford the corresponding ketone product, which was identified by comparison with the authentic sample through NMR and GC analysis.
96%	With 1-methyl-1H-imidazole; [2,2]bipyridinyl; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; tetrakis(acetonitrile)copper(I) trifluoromethanesulfonate; sodium chloride; In neat (no solvent);Milling; Green chemistry;	General procedure: 2,2,6,6-Tetramethylpiperidine 1-oxyl (TEMPO, 9.4 mg,0.06 mmol, 3 mol %), 2,2?-bipyridyl (9,4 mg, 0.06 mmol,3 mol %), [Cu(CN)4]OTf (22.6 mg, 0.06 mmol, 3 mol %) and1-methylimidazole (NMI, 11.5 mg, 11.2 muL, 0.14 mmol,7 mol %) were placed in a zirconia-milling beaker (45 mL)equipped with four balls (two balls × 5 mm , two balls ×12 mm ) of the same material. The jar was sealed and ballmilled for 1 min. Then, benzyl alcohol (216.3 mg, 207 muL,2.0 mmol), NaCl (1.0 g) together with other two zirconia balls(12 mm ) were added and the reaction mixture was subjectedto grinding for further 10 minutes overall (two cycles of5 minutes each). The first milling cycle was followed by a breakof 2 min leaving in the meantime the uncovered jar in open air.The progress of the reaction was monitored by TLC analysis(heptane/AcOEt 9:1 v/v) and GC-MS analysis on an aliquot ofthe crude. Upon completion of the ball milling process, the jarwas opened, the milling balls were removed and the resultingcrude product (adsorbed on NaCl) was then easily transferredinto a separating funnel filled with an aqueous 10% citric acidsolution (20 mL). The aqueous phase was extracted withcyclopentyl methyl ether (or alternatively with AcOEt)(3 × 15 mL). The combined organic fractions were washed withH2O (25 mL) and brine (25 mL), then dried over Na2SO4, andconcentrated in vacuo to give benzaldehyde in high yield (195 mg, 92%) and good purity (>93% by GC analysis). Alternatively, after completion of the reaction, the resulting crudeproduct (adsorbed on NaCl) can be also easily purified by ashort column chromatography on silica gel using heptane/ethylacetate (9:1 v/v) as the eluents to afford pure aldehyde 2b inhigh yield (202 mg, 95%) as a colourless liquid.
94%		General procedure: Firstly, GO (0.01 g) was added into water (3 mL) and the mixturecould generate the stable colloidal suspensions under a mild ultrasonictreatment. Afterwards, the alcohol (2 mmol) and (NH4)5H5[H2(WO4)6](0.03 mmol, M=1602) were added. The mixture was stirred for 15 min atroom temperature. Subsequently, hydrogen peroxide (30 wt%, 8 mmol)was added dropwise and the mixture was heated to 70C until thereaction was fully completed (monitored by TLC). After the reactioncompleted, GO could be readily separated from the mixtures bycentrifugation, and then ethyl acetate was added to the mixture to extract organic constituents. Finally, the organic extracts were concentratedunder reduced pressure and purified by column chromatography.

93%	With [Cu6(SC5H4N)6]; potassium hydroxide; In toluene; at 70℃; for 24h;Glovebox; Inert atmosphere;	In the glove box, the -1 - methyl methyl phenyl ethyl alcohol (1.0 mmol), [Cu6 (Pyt)6 ] (0.1 mmol), KOH (1.0 mmol) is added to the test tube with the magnetic coil in the has, then adding 2.0 ml dry toluene solvent. After the sealed reaction tube, is taken out of the glove box. Toward the nozzle leads into the small and stable and low production, stable air flow after such as, for 70 C reaction under 24 h; after the reaction, extracted with ethyl acetate (3 × 5 ml), the combined organic phase, dried with anhydrous sodium sulfate, filtered, concentrated filtrate for rotary evaporator, and then separating and purifying column law silica gel chromatography, to obtain the target product methyl methyl acetophenone (yield 93%).
93%	With 2,6-dimethylpyridine; 9-azabicyclo<3.3.1>nonane-N-oxyl; sodium perchlorate; In acetonitrile; for 8.66h;Inert atmosphere; Electrochemical reaction;	General procedure: The preparative electrolysis experiments were conducted with in an undivided cell containing0.1 M NaClO4-CH3CN solution (15 mL), alcohol substrate (1.0 mmol), ABNO (0.1 mmol),and 2,6-lutidine (1.0 mmol) at a constant current of 10.0 mA with moderate magnetic stirring for8.5 h in the atmosphere. Two square platinum sheets were employed as the anode and cathode,respectively. The electrolytic reaction was monitored by gas chromatography (GC) on a GC-2010system (Shimadzu, Kyoto, Japan) equipped with a SH-Rtx-Was polar column and a flame ionizationdetector (FID). Both the injector and detector were maintained at 220 C, the carrier gas is nitrogen,and the flow rate is 1.2 mL/min. The initial oven temperature of 100 C was held for 2 min andthen ramped up at 15 C per min to 220 C. This final temperature was held for 8 min. After thereaction was finished, the resulting mixture was concentrated in a rotary evaporator (Heidolph,Schwabach, Germany) and purified by column chromatography on silica gel using petroleum andethyl acetate 15:1) as eluent to afford the products. The products were confirmed by GC-MS, 1H-NMR,and 13C-NMR. NMR spectroscopy was carried out on a Bruker Avance III spectrometer (Bruker,Faellanden, Switzerland). The GC-MS analysis was measured on Thermo Trace ISQ instrument (ThermoFisher Nicolet,Waltham, MA, USA) with TG 5MS capillary column.Acetophenone (colorless oil, yield 80%):
79%	With C19H20IrNO2; sodium hydroxide; In water; at 140℃; for 48h;Inert atmosphere;	General procedure: In a flask under argon atmosphere, iridium catalyst 5 (0.50 or 1.0 mol %), sodium hydroxide (0.50 or 1.0 mol %), water (2 mL), and alcohol (2.0 mmol) were placed. The mixture was stirred under vigorous reflux (temperature of the oil bath was set at 140 C) for 20-96 h. After cooling to room temperature, water (4 mL) was added and the mixture was transferred to a separate funnel. Extraction of the organic compounds with dichloromethane (15 mL x 3), dehydration with sodium sulfate, followed by evaporation under vacuum gave crude mixture. For entries 2-11,the conversion of starting alcohol and the yield of ketone were determined by 1H NMR analysis in chloroform-d using triphenylmethane as an internal standard. For entries 1 and 12-14, the conversion of starting alcohol and the yield of ketone were determined by GC analysis using biphenyl as an internal standard. For entries 2-8, 10, and 11, the product was isolated by silica-gel column chromatography (eluent:ethyl acetate/ hexane).
70%	With indium(III) triflate; chloroamine-T; In acetonitrile; for 2h;Reflux; Inert atmosphere;	General procedure: The starting 1-(paratolyl)ethanol (1 mmol), chloramine-T (1 mmol), and In(OTf)3(0.3 mmol) were dissolved in CH3CN (10 mL) in a 100 mLflask equipped with a magnetic stirrer and a reflux condenser.The reaction mixture was heated at reflux for 3 h under anArgon atmosphere and was monitored for completion by TLC.After the reaction mixture was cooled to room temperature,the solvent was removed via rotary evaporation. The residueof the reaction mixture was separated through flash columnchromatography on silica gel. The obtained product was confirmed by spectroscopy.
	With manganese(IV) oxide; silica gel; In acetonitrile; at 70℃; for 8h;Molecular sieve;	General procedure: The above secondary alcohol was dissolved in acetonitrile (30mL). Molecular sieve (1.5g), silica gel (1.5g) and activated MnO2 (3.5g, 40mmol) were added, and the mixture was stirred at 70C for 8h. upon completion of the oxidation, the resulting suspension was filtered through diatomite, and the filtrate was concentrated by rotary evaporation. Purification of the residue by column chromatography (petroleum ethrt/EtOAc, 15:1) afforded ketone 13.

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 1585 - 1588
[2]Chemistry - A European Journal,2012,vol. 18,p. 11550 - 11554
[3]Chemical Science,2019,vol. 10,p. 4883 - 4889
[4]Bulletin of the Chemical Society of Japan,1989,vol. 62,p. 4069 - 4071
[5]Beilstein Journal of Organic Chemistry,2017,vol. 13,p. 2049 - 2055
[6]Organometallics,2018,vol. 37,p. 584 - 591
[7]Synlett,2018,vol. 29,p. 447 - 451
[8]Journal of Organic Chemistry,1997,vol. 62,p. 4916 - 4920
[9]ChemCatChem,2017,vol. 9,p. 1113 - 1118
[10]Patent: CN106588957,2017,A .Location in patent: Paragraph 0033
[11]Molecules,2019,vol. 24
[12]Bulletin of the Chemical Society of Japan,1990,vol. 63,p. 2433 - 2434
[13]Green Chemistry,2016,vol. 18,p. 4605 - 4610
[14]Advanced Synthesis and Catalysis,2018,vol. 360,p. 4293 - 4300
[15]Applied Organometallic Chemistry,2016,vol. 30,p. 645 - 652
[16]ACS Catalysis,2014,vol. 4,p. 3994 - 4003
[17]ACS Catalysis,2017,vol. 7,p. 7226 - 7230
[18]Chemistry Letters,2017,vol. 46,p. 808 - 810
[19]Organic Letters,2007,vol. 9,p. 109 - 111
[20]ACS Catalysis,2014,vol. 4,p. 2889 - 2895
[21]Chemical and Pharmaceutical Bulletin,2017,vol. 65,p. 801 - 804
[22]Justus Liebigs Annalen der Chemie,1915,vol. 408,p. 244
Chemische Berichte,1916,vol. 49,p. 2400
[23]Journal of the Chemical Society,1957,p. 5087
[24]Russian Journal of General Chemistry,2014,vol. 84,p. 2016 - 2020
Zh. Obshch. Khim.,2014,vol. 84,p. 2016 - 2020,5
[25]Journal of Organic Chemistry,2015,vol. 80,p. 10769 - 10776
[26]Organometallics,2017,vol. 36,p. 3638 - 3644
[27]Chemical Science,2017,vol. 8,p. 7476 - 7482
[28]Inorganic Chemistry,2017,vol. 56,p. 11282 - 11298
[29]Organometallics,2018,vol. 37,p. 603 - 617
[30]Organometallics,2018,vol. 37,p. 2732 - 2740
[31]European Journal of Medicinal Chemistry,2018,vol. 159,p. 90 - 103
[32]Inorganic Chemistry,2019,vol. 58,p. 4945 - 4953
[33]Canadian Journal of Chemistry,1965,vol. 43,p. 479

2
[ 100-52-7 ]
[ 585-74-0 ]
[ 13565-44-1 ]

Yield	Reaction Conditions	Operation in experiment
89%	Stage #1: 3-Methylacetophenone With sodium hydroxide In ethanol; water at 0℃; for 0.0833333h; Stage #2: benzaldehyde In ethanol; water for 0.0833333h;
89%	With sodium hydroxide In ethanol; water for 4h; Cooling with ice;	Preparation of the Chalcones General procedure: An Illustrative Procedure with (E)-1-Aryl-3-(2-pyrrolyl)-2-propenones (3k). 2-Pyrrolecarbaldehyde (12 mmol), acetophenone (13 mmol), and 24 mmol of NaOH in ethanol (20 mL) and water (10 mL) were mixed in an ice-bath and stirred for 4 h in the bath. The mixture was neutralized with 1 M-HCl aqueous solution to pH 8-9. The resulting precipitate was collected and recrystallized from ethanol.
78.9%	With barium(II) hydroxide In ethanol at 20℃;

42%	With potassium hydroxide; water In methanol for 24h;
	With hydrogenchloride

Reference： [1]Thomson, Connor J.; Barber, David M.; Dixon, Darren J. [Angewandte Chemie - International Edition, 2019, vol. 58, # 8, p. 2469 - 2473][Angew. Chem., 2019, vol. 131, # 8, p. 2491 - 2495,5]
[2]Jeong, Eun Jeong; Lee, In-Sook Han [Bulletin of the Korean Chemical Society, 2019, vol. 40, # 7, p. 668 - 673]
[3]Wu, Yufeng; Zhou, Guangli; Meng, Qingwei; Tang, Xiaofei; Liu, Guangzhi; Yin, Hang; Zhao, Jingnan; Yang, Fan; Yu, Zongyi; Luo, Yi [Journal of Organic Chemistry, 2018, vol. 83, # 21, p. 13051 - 13062]
[4]Stahl, Ingfried; Schomburg, Sabine; Kalinowski, Hans Otto [Chemische Berichte, 1984, vol. 117, # 6, p. 2247 - 2260]
[5]Lyle; Paradis [Journal of the American Chemical Society, 1955, vol. 77, p. 6667]

3
[ 77287-34-4 ]
[ 585-74-0 ]
[ 70138-19-1 ]

Reference： [1]Journal of the American Chemical Society,1936,vol. 58,p. 1808,1810
Organic Syntheses,1943,vol. Coll. Vol. II,p. 503,505

4
[ 585-74-0 ]
[ 620-14-4 ]

Reference： [1]Journal of Organic Chemistry,2018,vol. 83,p. 11067 - 11073
[2]Justus Liebigs Annalen der Chemie,1919,vol. 419,p. 111

5
[ 585-74-0 ]
[ 73318-83-9 ]

Yield	Reaction Conditions	Operation in experiment
89%	With tris(2,2'-bipyridyl)ruthenium dichloride; dioxane dibromide; sodium L-ascorbate In acetonitrile at 20℃; for 8h; Irradiation; Green chemistry;	General procedure for the visible light mediated oxidation of acetoarylones General procedure: To an oven-dried round bottom flask equipped with a magnetic stir bar was charged with dioxane dibromide (1.1 equiv.), tris(2,2′-bipyridyl)ruthenium(II) chloride (2 mol%), acetoarylone (AA, 1.0 equiv.), sodium ascorbate (3.0 equiv.) and dry CH3CN. The mixture was irradiated under a 5W Blue LED bulb at a distance of 5 cm under open-air atmosphere. After stirring at room temperature for 8-10 h, the solvent was removed under reduced pressure and the residue was purified by either recrystallization or filtration thru short pad silica gel column chromatography using hexane-ethyl acetate mixtures. The purity of the compound was confirmed by IR, 1H and 13CNMR measurements, vide infra.
	With 1,4-dioxane; selenium(IV) oxide
	With selenium(IV) oxide In 1,4-dioxane; water for 4h; Heating;

	With selenium(IV) oxide In methanol
	With selenium(IV) oxide In 1,4-dioxane; water
	With selenium(IV) oxide In 1,4-dioxane; water at 100 - 102℃;
	With pyridine; selenium(IV) oxide at 110℃; Inert atmosphere;	General procedure for the synthesis of substrates General procedure: Substrate 1a were synthesized from commercially available racemic phenylglycine methyl ester, while other substrates 1b-n were synthesized from related acetophenone derivatives according to the reported procedures.19 A mixture of acetophenone derivative (30mmol) and selenium dioxide (5.0g, 45mmol) in pyridine (15mL) was stirred at 110°C under nitrogen atmosphere overnight. After cooling to room temperature, 4Å molecular sieves (1.8g) and methanol (20mL) were added and the mixture was stirred for additional 10min. Then thionyl chloride (11.3mL, 150mmol) was added dropwise over 1h in an ice-water bath and stirred at room temperature for 12h. Perchloric acid (12mL, 150mmol) in acetonitrile (240mL) and deionized water (24mL) (1:20:2 in volume ratio) were added into the flask, and the mixture was stirred for at least 0.5h. Excess acid was neutralized by saturated sodium bicarbonate, then the mixture was filtrated. After removing the organic solvent by evaporation, the aqueous phase was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuum. The crude product was purified by flash chromatography (silica gel, petrol ether/ethyl acetate=10/1) to obtain arylglyoxylate.19a A mixture of above obtained arylglyoxylate (20mmol), anhydrous sodium acetate (2.0g, 24mmol), hydroxylamine hydrochloride (2.2g, 32mmol) and methanol (70mL) was heated to 60°C for 3h. After evaporating the organic solvent under vacuum, ethyl acetate was added to the resulting residue and the mixture was washed with water. The organic layer was then washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated in vacuum to afford oxime. To a solution of oxime (20mmol) and formic acid (24mL) in methanol (40mL) and water (24mL) at 0°C was added Zn dust (3.8g, 60mmol) portion-wise over 1h. The suspension was stirred for 3h at 0°C and an additional 4h at room temperature. The mixture was filtered through Celite and washed with methanol. The filtrate was concentrated and the resulting residue was purified by flash chromatography (silica gel, dichloromethane/methanol=10/1) to afford the racemic arylglycine ester.19b The above obtained arylglycine ester (10mmol) and anhydrous magnesium sulfate (1.2g) were stirred together in dichloromethane (50mL) at room temperature for 20min. Then the aldehyde (10mmol) and triethylamine (8mL) were added sequentially and dropwise. After stirred for 12h at the same temperature, the resulting mixture was filtered and the organic solvent was evaporated in vacuum. The residue was dissolved in ethyl acetate (20mL) and water (20mL), and the separated aqueous layer was extracted with ether (2×20mL). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated in vacuum. The residue was purified by flash chromatography (silica gel, petrol ether/triethylamine=50/1 to 20/1) to afford the substrate for hydrogenation as a white solid.19c
	With selenium(IV) oxide In 1,4-dioxane; water Reflux;
	With selenium(IV) oxide; water In 1,4-dioxane Reflux;
	With selenium(IV) oxide In 1,4-dioxane; water at 110℃; for 4h; Inert atmosphere;
	With selenium(IV) oxide; water In 1,4-dioxane for 6h; Reflux;
	With iodine; dimethyl sulfoxide In chlorobenzene at 120℃;
	With selenium(IV) oxide; water In 1,4-dioxane for 12h; Reflux;
	With selenium(IV) oxide; water In 1,4-dioxane Inert atmosphere; Schlenk technique; Reflux;
	With selenium(IV) oxide In 1,4-dioxane; water at 70℃;
	With selenium(IV) oxide; water In 1,4-dioxane Reflux;	Preparation of -Cyanoenones 8b-m; General Procedure General procedure: To a 100 mL two-neck round-bottom flask, SeO2 (2.00 g, 18.0 mmol), H2O (0.31 g, 17.0 mmol) and 1,4-dioxane (10.0 mL) were added and the flask was fitted with a condenser. The mixture was heated to reflux with stirring until the solid dissolved. Then, substituted aryl ketone(10.0 mmol) was added into the solution and the reaction mixture was allowed to reflux. After the reaction was completed, the reaction mixture was cooled to r.t. and filtered through a Celite pad,which was then washed several times with diethyl ether. The combined filtrate was evaporated on a rotary evaporator to afford the crude product, which was used in the next step without further purification. A solution of aryllglyoxal monohydrate (10.0 mmol) in benzene (40 mL) was heated under reflux with azeotropic removal of water (Dean-Stark). Thereafter, cyanomethylidenetriphenylphosphorane(3.80 g, 12.6 mmol) and benzoic acid (211 mg, 1.73 mmol) were added and the mixture was stirred for 10 h under an argon atmosphere at 80 °C. The cooled mixture was concentrated in vacuo and the residue was subjected to column chromatography on silica gel (hexane/EtOAc, 2:1) and recrystallization to give 8 as yellow crystals.
	With selenium(IV) oxide In 1,4-dioxane; water at 95℃; Inert atmosphere; Schlenk technique;

Reference： [1]Natarajan, Palani; Manjeet; Kumar, Naveen; Devi, Sapna; Mer, Kalyani [Tetrahedron Letters, 2017, vol. 58, # 7, p. 658 - 662]
[2]Eastham; Feeney [Journal of Organic Chemistry, 1958, vol. 23, p. 1826,1828]
[3]Nakamura, Akira; Ataka, Toshiei; Segawa, Hirozo; Takeuchi, Yasutomo; Takematsu, Tetsuo [Agricultural and Biological Chemistry, 1983, vol. 47, # 7, p. 1555 - 1560]
[4]Konno, Shoetsu; Osawa, Noriko; Yamanaka, Hiroshi; Sanemitsu, Yuzuru; Kawamura, Shinichi; Sakaki, Masaharu [Journal of Agricultural and Food Chemistry, 1995, vol. 43, # 3, p. 838 - 842]
[5]Mupparapu, Nagaraju; Khan, Shahnawaz; Battula, Satyanarayana; Kushwaha, Manoj; Gupta, Ajai Prakash; Ahmed, Qazi Naveed; Vishwakarma, Ram A. [Organic Letters, 2014, vol. 16, # 4, p. 1152 - 1155]
[6]Hameed, Abdul; Zehra, Syeda T.; Shah, Syed J. A.; Khan, Khalid M.; Alharthy, Rima D.; Furtmann, Norbert; Bajorath, Jürgen; Tahir, Muhammad N.; Iqbal, Jamshed [Chemical Biology and Drug Design, 2015, vol. 86, # 5, p. 1115 - 1120]
[7]Fan, Dongyang; Lu, Jian; Liu, Yang; Zhang, Zhenfeng; Liu, Yangang; Zhang, Wanbin [Tetrahedron, 2016, vol. 72, # 35, p. 5541 - 5547]
[8]Gupta, Swati; Kushwaha, Bhavana; Srivastava, Akansha; Maikhuri, Jagdamba Prasad; Sankhwar, Satya N.; Gupta, Gopal; Dwivedi, Anil Kumar [RSC Advances, 2016, vol. 6, # 80, p. 76288 - 76297]
[9]Wu, Hua; Wang, Qian; Zhu, Jieping [Angewandte Chemie - International Edition, 2017, vol. 56, # 21, p. 5858 - 5861][Angew. Chem., 2017, vol. 129, # 21, p. 5952 - 5955]
[10]Hossian, Asik; Manna, Manash Kumar; Manna, Kartic; Jana, Ranjan [Organic and Biomolecular Chemistry, 2017, vol. 15, # 31, p. 6592 - 6603]
[11]Hung, Chen-Hsun; Gandeepan, Parthasarathy; Cheng, Lin-Chieh; Chen, Liang-Yu; Cheng, Mu-Jeng; Cheng, Chien-Hong [Journal of the American Chemical Society, 2017, vol. 139, # 47, p. 17015 - 17021]
[12]Xu, Liang; Wang, Shengpeng; Chen, Bajin; Li, Meichao; Hu, Xinquan; Hu, Baoxiang; Jin, Liqun; Sun, Nan; Shen, Zhenlu [Synlett, 2018, vol. 29, # 11, p. 1505 - 1509]
[13]Yu, Qi-Wen; Wu, Lu-Ping; Kang, Tian-Chen; Xie, Jin; Sha, Feng; Wu, Xin-Yan [European Journal of Organic Chemistry, 2018, vol. 2018, # 29, p. 3992 - 3996]
[14]Goti, Giulio; Bieszczad, Bartosz; Vega-Peñaloza, Alberto; Melchiorre, Paolo [Angewandte Chemie - International Edition, 2019, vol. 58, # 4, p. 1213 - 1217][Angew. Chem., 2019, vol. 131, # 4, p. 1226 - 1230,5]
[15]Teng, Lili; Liu, Xiang; Guo, Pengfeng; Yu, Yue; Cao, Hua [Organic Letters, 2020, vol. 22, # 10, p. 3841 - 3845]
[16]Akutsu, Hiroshi; Nakashima, Kosuke; Kanetsuna, Yuta; Kawada, Masahiro; Hirashima, Shin-Ichi; Miura, Tsuyoshi [Synthesis, 2020, vol. 52, # 24, p. 3874 - 3880]
[17]Lipp, Alexander; Badir, Shorouk O.; Dykstra, Ryan; Gutierrez, Osvaldo; Molander, Gary A. [Advanced Synthesis and Catalysis, 2021, vol. 363, # 14, p. 3507 - 3520]

6
[ 585-74-0 ]
[ 7287-81-2 ]

Yield	Reaction Conditions	Operation in experiment
96%	With iron(III) chloride; C6H13BN2; In dichloromethane; at 20℃;	General procedure: To a solution of ketone (0.25 mmol) in DCM (1 mL) was added NHC-BH3 4 (24-27 mg, 0.2-0.25 mmol) and anhydrous FeCl3 (0.125-0.25 mmol) at room temperature, the mixture was stirred for 30 min-1 h. The residue was dried in vacuo and purified by flash column chromatography (silica gel) to give the corresponding alcohols 9a-r.
96%	With isopropyl alcohol; sodium hydroxide; for 3h;Inert atmosphere; Schlenk technique; Reflux;	General procedure: Under nitrogen atmosphere, a mixture of ketone (2 mmol), catalyst 4 (0.008 mmol), and 2-propanol (17.6 mL) was stirred at 82C. After 5 min, 2.4 mL of 0.1 M NaOH (0.24 mmol) solution in 2-propanol was introduced to initiate the reaction, and the reaction mixture was stirred at refluxing temperature. At the specified time, 0.1 mL of the reaction mixture was filtered through a short pad of celite to remove the complex catalyst, and immediately diluted with 0.2 mL of 2-propanol. The filtrate was used for GC analysis. After the reaction was finished, the mixture was condensed under reduced pressure and subject to flash silica gel column chromatography to afford the alcohol product (detected under 254 nm UV light or by alkaline potassium permanganate solution; eluent: petroleum ether (60-90 C)/ethyl acetate = 10:1 or petroleum ether (30-60 C)/dichloromethane= 1:1, v/v). The alcohol products were identified by comparison with the authentic sample through NMR and GC analyses.
95%	With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H2O); isopropyl alcohol; at 82℃; for 6h;Inert atmosphere; Green chemistry;	The 3 - methyl acetophenone (134 mg, 1.0 mmol), cat. [Ir] (1.1 mg, 0 . 002 mmol, 0.2 muM %) and isopropyl alcohol (5 ml) are added to the 25 ml Kjeldahl tube, N2Protection , 82 C reaction 6 h. Cooling to room temperature, rotary evaporation to remove the solvent, then through the column chromatography (developing solvent: petroleum ether/ethyl acetate) to obtain the pure target compound, yield: 95%

94%	With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H2O); hydrogen; In tert-Amyl alcohol; at 30℃; under 760.051 Torr; for 12h;Green chemistry;	General procedure: To an oven-dried 5 mL round-bottom flask were added ketone (1 mmol), cat. 7 (2.7 mg, 0.5 mol %) and tert-amyl alcohol (1 mL). Next, vacuum was applied to the flask followed by filling with H2 gas and keeping the flask attached to a balloon filled with H2 gas. The mixture was heated at 30 C for 12 h. After completion of the reaction, the solvent was removed by evaporation under reduced pressure. The alcohols were isolated and purified by filtering a hexanes/ethyl acetate (5:1) solution of the crude product through a pad of silica gel, and then removing the solvent under reduced pressure. The conversion and purity of the alcohol products was assessed using NMR spectroscopy.
94%	With C44H40ClN2NiP2(1+)*F6P(1-); hydrogen; potassium hydroxide; In isopropyl alcohol; at 120℃; under 30003 Torr; for 12h;Autoclave;	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.
91%	With sodium tetrahydroborate; In methanol; at 20℃; for 1.5h;Cooling with ice;	To a solution of 3?-methylacetophenone (1.98 g, 14.8mmol) in dry MeOH (30 mL) was added NaBH4 (690 mg, 18.2 mmol) in an ice bath. Themixture was stirred at room temperature for 1.5 h. The reaction was quenched with H2O.MeOH was removed under reduced pressure. The product was extracted with EtOAc (20 mL× 3), and washed with brine (30 mL × 1). The mixture was dried over Na2SO4 andconcentrated. Purification by silica gel column chromatography (hexane/EtOAc (5:1))afforded 1c as a colorless oil (1.82 g, 91%).
99%Spectr.	With hydrogen; In 1-butyl-3-methylimidazolium hexafluorophosphate; at 20℃; under 760.051 Torr; for 30h;	General procedure: The palladium nanoparticles on SWNTs were prepared in [BMIM][PF6]. The SWNTs (5 mg) was grounded in IL (1 ml) for 30 min, and then Pd(II) acetate (0.018 mmol) was dissolved in the solution. The Pd(II) acetate was in situ reduced in IL with 1 atm of hydrogen for 5 min at room temperature. The aryl ketone (0.3 mmol) was added to this solution under 1 atm of hydrogen at room temperature. After the >99% completion of the reaction was checked by TLC, the products were extracted with ethyl ether. The ethereal phase was concentrated and analyzed by 1H NMR.
85%Spectr.	With bis(2-hydroxyethyl)ammonium formate; palladium dichloride; at 20℃; for 24h;Inert atmosphere;	General procedure: (Table 2, entry 4): To a solution of acetophenone (1) (120 mg, 1.00 mmol) in [BHEA][HCO2] (5.00 mL, 39.7 mmol) was added PdCl2 (17,7 mg, 10.0 mol%) at rt and the mixture was stirred at the same temperature for 6 h under argon atmosphere. The mixture was poured into brine (10 mL) and extracted with EtOAc (10 × 10 mL). The organic layer was washed with brine (100 mL) and dried with MgSO4. After removal of the solvent, the residue was subjected to column chromatography (Merck kieselgel 60, phi = 2.0 cm, l = 11.5 cm; EtOAc-hexane, 1:5) to give 1-phenylethanol (2) as colorless oil; yield: 110 mg (90%).
85%Spectr.	With bis(2-hydroxyethyl)ammonium formate; palladium dichloride; at 20℃; for 24h;Inert atmosphere;	General procedure: To a solution of 4'-(trifluoromethyl)acetophenone (3e) (188 mg, 1.00 mmol) in DMF (5.00 mL) was added [BHEA][HCO2] (5.00 mL, 39.7 mmol) and PdCl2 (35.5 mg, 20.0 mol %) at rt and the reaction mixture was stirred at the same temperature for 2 h under argon atmosphere. The mixture was poured into brine (10 mL) and extracted with Et2O (10 10 mL). The organic layer was washed with brine (150 mL) and dried with MgSO4. After removal of the solvent, the residue was subjected to column chromatography (Merck Kieselgel 60, Phi=2.0 cm, l=7.5 cm; EtOAc-hexane, 1:5) to give 1-(4-trifluoromethylphenyl)ethanol (4e) as colorless oil; yield: 174 mg (91%).
	With C43H41Cl2N3P2Ru; isopropyl alcohol; sodium t-butanolate; for 0.0166667h;Inert atmosphere; Reflux;Catalytic behavior;	General procedure: Under a nitrogenatmosphere, the aromatic ketone (2 mmol), NaOtBu (0.1 mL, 0.1 M) andcomplex 8a (1.6 mg, 0.002 mmol) were dissolved in degassed 2-propanol(20 mL) and the mixture was refluxed. The hydrogenation of the ketone beganinstantly, and the extent of conversion was determined by GC analysis.
	With isopropyl alcohol; potassium hydroxide; for 2h;Inert atmosphere; Reflux;	General procedure: Under nitrogen atmosphere, aromatic ketone (1mmol), KOH (1mL, 0.1M) and complex 2 (1mg, 0.003mmol) were dissolved in degassed 2-propanol (9.75mL) with nitrogen and the mixture was refluxed for 180min. The same reaction conditions were used for complex 4 (10mg) and complex 5 (10mg). They were added in degassed 2-propanol as solid. The hydrogenation of the ketone was followed by GC using HP-5 column.
	With [ruthenium(II)(eta6-1-methyl-4-isopropyl-benzene)(chloride)(mu-chloride)]2; (1R,2R)-1,2-bis(4'-(diphenylphosphino)phenyl)-1,2-dimethoxyethane; potassium tert-butylate; In isopropyl alcohol; at 82℃; for 24h;Inert atmosphere; Schlenk technique;	General procedure: A mixture of [Ru(p-cymene)Cl2]2 (0.004 mmol) and correspondingchiral bisphosphine ligand (1e6) (0.004 mmol) in iPrOH(7 ml) were placed under a nitrogen atmosphere in a standardSchlenk tube. The reaction mixture was heated and stirred undernitrogen at 82 C for 2 h. After cooling to room temperature, thearomatic ketone (1 mmol) was added to this mixture and the solutionwasthen heated to 82 C. To initiate the reaction, the solutionof tBuOK (0.05 mmol) in iPrOH was added to the stirring reactionmixture. To monitor the conversions of ketones to correspondingsecondary alcohols, a small volume of reaction mixture was takenfrom Schlenk tube via micro syringe and diluted with iPrOH, andthen passed from microfilter. The conversion and enantiomericexcess were monitored by GC using Agilent HP-Chiral 20B column.
95%Chromat.		General procedure: Under a nitrogen atmosphere, a mixture of ketone (2 mmol),catalyst 3 (0.01 mmol), and 2-propanol (18 mL) was stirred at 82 C for 10 min. Then, iPrOK solution in 2-propanol (2.0 mL,0.1 mol/L, 0.2 mmol) was introduced to initiate the reaction.The reaction mixture was stirred at reflux. After the statedtime, 0.1 mL of the reaction mixture was sampled and immediatelydiluted with 0.5 mL of 2-propanol precooled to 0 C, andfiltered through a short pad of celite to quench the reaction byremoving the complex catalyst. The resultant filtrate was usedfor GC analysis. After the reaction was finished, the mixture wascondensed under reduced pressure and subjected to flash silicagel column chromatography to afford the alcohol product. The alcohol products were identified by comparison with authenticsamples using NMR and GC analyses.
78%Chromat.	With Ru(3-(2-(diphenylphosphino)benzylideneamino)-2-(1-hydroxy-2-phenylethyl)quinazolin-4(3H)-one)2Cl2; sodium hydroxide; In isopropyl alcohol; at 82℃; for 24h;Schlenk technique; Inert atmosphere;Catalytic behavior;	General procedure: A mixture of the Ru(II) complex (0.004 mmol), 2-propanol(3 mL), NaOH (0.1 mmol) and the substrate (2 mmol,substrate:catalyst/500:1) was introduced into a Schlenktube under an argon atmosphere. The resulting solution washeated at 82 C for 24 h. The solution was cooled downand then concentrated to dryness under reduced pressure.The residue was purified by flash chromatography (ethylacetate:hexane/1:10). The products were analyzed by GC.
	With [ruthenium(II)(eta6-1-methyl-4-isopropyl-benzene)(chloride)(mu-chloride)]2; (4R,5R)-4,5-bis(3-(diphenylphosphino)phenyl)-2,2-dimethyl-1,3-dioxolane; potassium hydroxide; In isopropyl alcohol; at 82℃; for 24h;Inert atmosphere; Schlenk technique;	General procedure: A mixture of [Ru(p-cymene)Cl2]2 (0.004 mmol) andcorresponding chiral bisphosphine ligand (7-12)(0.004 mmol) in iPrOH (7 mL) were placed under a nitrogenatmosphere in a standard Schlenk tube. The reactionmixture was heated and stirred under nitrogen at 82 C for2 h. After cooling to room temperature, the aromaticketone (1 mmol) was added to this mixture and the solutionwas t hen h eated to 82 C. To initiate the reaction, thesolution of t-BuOK (0.05 mmol) in iPrOH was added to thestirring reaction mixture. To monitor the conversions ofketones to corresponding secondary alcohols, a smallvolume o f reaction mixture w as taken from Schlenk t ubevia micro syringe and diluted with iPrOH, and then passedfrom microfilter. The conversion and enantiomeric excesswere monitored by GC using Agilent HP-Chiral 20B column.
> 99%Chromat.	With borane-ammonia complex; In methanol; water; at 20℃; for 0.0833333h;	General procedure: mpg-C3N4/Pd (4 mg) and the ketone or aldehyde (0.35 mmol)were suspended in methanol/water mixture (2 mL, 1:1) in apressure tube. Subsequently, AB (0.75 mmol) was addedand the solution was magnetically stirred for 2 (for aldehydes)or 5 min (for ketones) at room temperature. Aftercompletion of the reaction, the catalyst was filtered andwashed with methanol for further use. The solvent wasremoved under the reduced pressure. The yield of each alcoholwas determined by gas chromatography-mass spectrometry(GC-MS).

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7
[ 585-74-0 ]
[ 61560-94-9 ]

Yield	Reaction Conditions	Operation in experiment
100%	With selenium(IV) dioxide In pyridine for 3.5h; Heating / reflux;	55 To 3-methylacetophenone (5.0 g, 37 mmol) in pyridine (50 ml) was added selenium dioxide (7.44 g, 67 mmol), and the mixture was refluxed for 3.5 hours. The resulting black solid was filtered off. The filtrate was neutralized with concentrated hydrochloric acid and extracted with ether to give 3-methylphenylglyoxylic acid (6.12 g, 37 mmol, yield: 100%). Then to the obtained 3-methylphenyloxoacetic acid (4.0 g, 24 mmol) in methanol (250 ml) was added concentrated sulfuric acid (13 ml), and the mixture was refluxed for 5 hours. After being neutralized with saturated sodium hydrogencarbonate, the solution was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated. The residue was purified by column chromatography (SiO2 170 g, eluting solvent: Hex/AcOEt = 200/1 ~ 0/1) to give the captioned compound (3.75 g, 16.7 mmol, yield: 69%) as a pale yellow oil.
90%	With pyridine; selenium(IV) dioxide at 90 - 110℃; for 4h; Inert atmosphere;
87%	With pyridine; selenium(IV) dioxide at 110℃; for 4h; Schlenk technique; Inert atmosphere;

54%	With pyridine; selenium(IV) dioxide at 90 - 110℃; for 5h; Inert atmosphere;
53%	With pyridine; selenium(IV) dioxide at 110℃; for 12h; Inert atmosphere;
	With pyridine; selenium(IV) dioxide
	With pyridine; selenium(IV) dioxide
	With selenium(IV) dioxide
	With selenium(IV) dioxide In pyridine at 90℃; for 6h; Inert atmosphere;
	With pyridine; selenium(IV) dioxide
	With selenium(IV) dioxide
	With selenium(IV) dioxide
	With pyridine; selenium(IV) dioxide at 120℃; for 18h; Inert atmosphere;
	With selenium(IV) dioxide In pyridine at 90 - 110℃; for 6h; Schlenk technique;
	With selenium(IV) dioxide Inert atmosphere;
	With pyridine; selenium(IV) oxide
	With pyridine; selenium(IV) dioxide at 110℃; for 20h; Inert atmosphere;
	With pyridine; selenium(IV) dioxide at 90 - 110℃; for 5h; Inert atmosphere;
	With pyridine; selenium(IV) dioxide at 90 - 110℃; for 5h;
	With pyridine; selenium(IV) dioxide at 120℃; Inert atmosphere;
	With pyridine; selenium(IV) dioxide at 110℃; for 6h; Schlenk technique; Inert atmosphere;
	With pyridine; selenium(IV) oxide at 90 - 110℃; for 6h; Inert atmosphere;
	With pyridine; selenium(IV) dioxide at 90 - 110℃; for 5h; Inert atmosphere;
	With pyridine; selenium(IV) dioxide at 110℃; for 16h;
	With pyridine; selenium(IV) dioxide at 110℃; for 16h;	2.1.2 Oxidation of the corresponding aryl-ketones: General procedure: In a dry flask, flushed with nitrogen, aryl-ketone (1 equiv, 8 mmol) and selenium dioxide (2 equiv, 1.78 g, 16 mmol) were added followed by anhydrous pyridine (4 mL). The reaction mixture was then stirred at 110 °C for 16 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the solution containing precipitated selenium was filtered using a Buchner funnel, and the residue was washed with EtOAc (60 mL). The filtrate was treated with 1M aqueous NaOH (30 mL) and the aqueous layer was separated. This procedure was repeated 3 times and the aqueous layers were combined, then acidified with 1M aqueous HCl (pH=1.5). Thus, the mixture was extracted with EtOAc (3×60 mL) and the combined organic layers were washed with brine, dried over Na2SO4 and concentrated under reduced pressure to provide the corresponding α-ketoacid. Expected glyoxylic acid was isolated with quantitative yield (>99%) and was pure enough (>98%) to be used without further purification. Compounds 1h was obtained by this oxidation.

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8
[ 110-88-3 ]
[ 6091-44-7 ]
[ 585-74-0 ]
[ 78888-52-5 ]

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9
[ 134-62-3 ]
[ 917-54-4 ]
[ 585-74-0 ]

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10
[ 105-58-8 ]
[ 585-74-0 ]
[ 33166-79-9 ]

Yield	Reaction Conditions	Operation in experiment
84%	With sodium hydride; at 80℃; for 2h;	Sodium hydride (3.1g, 77.1mmol) and diethylcarbonate were added to 3- methyl acetophenone (4.5g, 33.54mmol). The reaction mixture was stirred for 2hrs with heating at 80C. Once the reaction was completed, ice water and acetic acid were added thereto. The resulting mixture was washed with saturated saline and extracted with ethyl acetate. The organic layer was separated, dried over anhydrous MgS04 and concentrated under a reduced pressure. The resulting residue was purified by flash chromatography to obtain 5.8g of the titled compound (yield: 84 %). @H-NMR (200MHz, CDC13) 8 7.83-7.63 (m, 2H) 7.42-7.28 (m, 2H) 4.27~4.18 (m, 2H) 3.97 (s, 2H) 2.40 (s, 3H) 1.36~1.23 (m, 3H)
84%	With sodium hydride; at 80℃; for 2h;	Sodium hydride (3.1 g, 77.1 mmol) and diethyl carbonate were combined with 3-methylacetophenone (4.5 g, 33.54 mmol). The mixture was stirred for 2 hours at 80C. After the reaction was completed, ice water and acetic acid were added thereto. Then, the mixture was extracted with ethyl acetate/saturated sodium chloride. The extract was dried over anhydrous magnesium sulfate, concentrated, and the resulting residue was purified by column chromatography to obtain 3-oxo-3-m-tolylpropionate ethyl ester (5.8 g, yield 84 %). ¹H NMR (200MHz, CDCl3) : No. 7.83-7.63 (m, 2H), 7.42-7.28 (m, 2H), 4.27-4.18 (m, 2H), 3.97 (s, 2H), 2.40 (s, 3H), 1.36-1.23 (m, 3H).
46.9%		Example 10; Ethyl 3-methyl-benzoyl-acetate (1 -10-a); To a vigorously stirred suspension of NaH (564 mg, 48.5 mmol) and CO(OEt)2 (5.73 g, 48.5 mmol) in anhydrous toluene (50ml) was added dropwise a solution of 3-methylacetophenone (4.33 g, 32.3 mmole) in toluene under reflux. The mixture was allowed to reflux and was stirred for 30 min after the addition was complete. When cooled to room temperature, the mixture was acidified with glacial AcOH. After ice-cold water was added, the mixture was extracted with toluene. The organic layer was dried over MgSO4, and evaporated. The residue was further chromatographed over silica gel by elution with CH2CI2-/i-haxane (3:2) to afford l-10-b as light-yellow liquid (3.13g, 46.9%) <n="35"/>1H-NMR (DMSO-t/6, 200 MHz): delta 7.68-7.72 (2H, m, H-4, H-6) , 7.32-7.36 (2H, m, H-2, H-3) , 4.16 (2H, q, J = 7, CH2CH3) , 3.94 (2H, s, H-10) , 2.38 (3H, s, CH3), 1.2 (3H, t, J = 7,CH2CHa) MS (m/z) 206 (El+) Anal, calcd for C12H14O3: C, 69.88; H, 6.84; Found: C, 69.72; H, 6.95.

Reference： [1]Journal of Medicinal Chemistry,2006,vol. 49,p. 1910 - 1915
[2]Patent: WO2005/100297,2005,A1 .Location in patent: Page/Page column 28-29
[3]Patent: WO2005/100303,2005,A1 .Location in patent: Page/Page column 56
[4]Chemical and Pharmaceutical Bulletin,1982,vol. 30,p. 2590 - 2594
[5]Angewandte Chemie - International Edition,2012,vol. 51,p. 8661 - 8664
[6]Patent: WO2008/70176,2008,A1 .Location in patent: Page/Page column 32-33
[7]Journal of Medicinal Chemistry,1997,vol. 40,p. 3049 - 3056
[8]European Journal of Organic Chemistry,2015,vol. 2015,p. 3656 - 3660
[9]Organic and Biomolecular Chemistry,2018,vol. 16,p. 4683 - 4687
[10]Molecules,2019,vol. 24
[11]Organic Letters,2019,vol. 21,p. 190 - 195
[12]Organic Letters,2020,vol. 22,p. 1222 - 1226

11
[ 585-74-0 ]
[ 537-92-8 ]

Yield	Reaction Conditions	Operation in experiment
93%	With O-trifluorobenzenesulfonyl-acetohydroxamic acid ethyl ester; toluene-4-sulfonic acid; In water; acetonitrile; at 20℃;Inert atmosphere;	General procedure: Table 2 shows the results of examining various catalysts in the reaction of synthesizing N- (2-naphthyl) acetamide from 2-acetonaphthone. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, methanesulfonic acid, tosylic acid monohydrate, trifluoromethanesulfonic acid, bistrifluoromethanesulfonimide, boron trifluoride diethyl ether complex, scandium (III) trifluoromethanesulfonate, trifluoromethanesulfone Iron (III) oxide, trifluoromethanesulfoCopper (II) trifluoromethanesulfonate, bismuth trifluoromethanesulfonate (III), titanium tetrachloride and iron trichloride have excellent effects (Entries 2 to 14).
34%	With nitromethane; trifluoromethylsulfonic anhydride; acetic acid; In formic acid; at 80 - 120℃;	Take a reaction tube, add 60-100mg (1.2mmol) of nitromethane, 35-45mg (0.3mmol) of m-methylacetophenone, 0.5mL of acetic acid,Trifluoromethanesulfonic anhydride 150-200mg (0.6mmol),30-60 mg (0.75 mmol) of formic acid, stirring at 80-120C for 1-72 hours. After the completion of the reaction, 10 mL of sodium hydroxide solution was added to quench the reaction, extracted with ethyl acetate 3 times, the organic phase was washed with 5 mL of brine, and the organic phases were combined and separated by column chromatography to obtain 15.2 mg of m-methylacetanilide with a yield of 34%.

Reference： [1]Patent: JP2018/135293,2018,A .Location in patent: Paragraph 0029; 0031
[2]Journal of Organic Chemistry,2018,vol. 83,p. 13080 - 13087
[3]Science,2020,vol. 367,p. 281 - 285
[4]Patent: CN112574054,2021,A .Location in patent: Paragraph 0161-0163
[5]Synthetic Communications,1992,vol. 22,p. 2125 - 2128

12
[ 585-74-0 ]
[ 51012-64-7 ]

Yield	Reaction Conditions	Operation in experiment
96%	With Oxone; ammonium bromide; In methanol; for 0.666667h;Reflux;	General procedure: Oxone (1.352 g, 2.2 mmol) was added to the well stirred solution of substrate (2 mmol) and NH4Br (0.215 g, 2.2 mmol) in methanol (10 ml) and the reaction mixture was allowed to stir at room temperature (or reflux temperature). After completion of the reaction, as monitored by TLC, the reaction mixture was quenched with aqueous sodium thiosulfate, and extracted with ethyl acetate (3×25 ml). Finally, the combined organic layer was washed with water, dried over anhydrous sodium sulfate, filtered and removal of solvent in vacuo yielded a crude residue, which was further purified by column chromatography over silica gel (finer than 200 mesh) to afford pure products. All the products were identified on the basis of 1H NMR and mass spectral data.
80%	With bromine; In 1,4-dioxane; diethyl ether; at 20℃; for 5h;	To a solution of 1-m-tolyl-ethanone (6.Og, 44.72mmol) in dioxane (5ml), bromine (7.14g, 44.72mmol) in dioxane (10ml) and ether (15ml) was added and stirred at room temperature for 5 hr. The reaction mixture was poured into ice water and the compound was extracted using ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, filtered and then evaporated to give crude 2- bromo- 1-m-tolyl-ethanone, 7.6g (80%). The crude compound obtained was used in the next step without further purification.
	With bromine; In diethyl ether; at 0℃;	Example 21: 4-[2,5-Dioxo-4-hydroxymethyl-3-methyl-4-(3-methylphenyl)imidazolidin-l-yl]-2- trifluoromethyl-benzonitrile (Method A)Step I: 2-bromo- 1 -(3-methylphenyl)ethanone; [00339] To a solution of l-(3-methylphenyl)ethanone (2 g) in ethyl ether (20 mL) is added bromine (726 muL) at 00C. The mixture is treated with an aqueous solution of sodium bicarbonate, extracted with ethyl ether, dried over magnesium sulfate, concentrated and purified on silica gel (ethyl acetate/cyclohexane 0/100) to give the desired compound.TLC: Fr = 0.42 (ethyl acetate/cyclohexane 10/90). delta 1H NMR (CDCl3): 2.47 (s, 3H); 4.49 (s, 2H); 7.40-7.47 (m, 2H); 7.81-7.91 (m, 2H).LCMS: (Rt = 3.42 min): not ionisable.

	With N-Bromosuccinimide; trimethylsilyl trifluoromethanesulfonate; In acetonitrile; at 40℃;Darkness;	General procedure: Ketone (1 eq) and N-bromosuccinimide (NBS) (2 eq) were solved in acetonitrile and trimethylsilyl trifluoromethanesulfonate (TMS-OTf) (1 eq) was added. The reactions were stirred at T = 40 C until completeness, diluted with diethyl ether (2 ml), washed with H2O (3 x 2 ml), dried over Na2SO4 and concentrated under reduced pressure. This procedure provided bromoketones intermediates in 75-90% overall yield, with purities generally >90% as determined by HPLC-MS. The compounds was used without further purification.
	With hydrogen bromide; bromine; acetic acid; at 0 - 5℃;	General procedure: General procedure to obtainalpha-bromoacetophenonederivatives Acetophenone derivative (10 mmol) was solved in acetic acid(50 mL) and hydrobromic acid (0.5 mL) mixture. Bromine(10 mmol, 0.52 mL) was added dropwise to this mixture at 0-5Ctemperatureandthemixturewasstirredfor6-7h.Afterthisperiod, the mixture was poured into ice-water, collapsed portionwas filtrated and after dryness it was crystallized from ethanol.
	With N-Bromosuccinimide; toluene-4-sulfonic acid; In acetonitrile; at 50℃; for 24h;	General procedure: Synthesis of alpha-Aminocarbonyl Compounds by a Two-Step Method. First Step Synthesis of alpha-bromoacetophenone: to a solution of the acetophenone derivative (15.0 mmol, 1 equiv) in 8 mL of acetonitrile were added NBS (2.72 g, 15.3 mmol, 1.02 equiv) and p-toluenesulfonic acid (2.85 g, 15.0 mmol, 1 equiv). The reaction mixture was stirred for 24 h at 50 C. After that time, the solvent was evaporated under reduced pressure. A water solution of saturated NaHCO3 (30 mL) was then added, and the solution was extracted with dichloromethane (3 × 30 mL). The organic layers were combined and dried over Na2SO4. The solvent was evaporated, and the residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate = 25:1, V/V) to afford the desired product in 82% yield as a white solid. After that, alpha-bromoacetophenone (5 mmol) and with aniline (5 mmol) and NaHCO3 (5 mmol) were added to a stirred solution of EtOH (20 ml) at room temperature for 12 h. The crude product was filtered under reduced pressure to give a yellow precipitate, which was recrystallized by EtOH and the yellow solid was isolated in 86% yield.
	With bromine; In chloroform; at 20℃; for 1h;Cooling with ice;	3-methylacetophenone (1.34 g, 10 mmol) was dissolved in 100 ml of chloroform.Br2 (1.91 g, 12 mmol) was slowly added dropwise under ice bath, and the mixture was stirred at room temperature for 1 h.After completion of the reaction, the reaction was quenched with saturated sodium sulfite, and the organic phase was washed with saturated sodium bicarbonate, and saturated brine.After dried over anhydrous sodium sulfate, the solvent was removed in vacuo to give a crude product 2.13g.

Reference： [1]Tetrahedron Letters,2012,vol. 53,p. 191 - 195
[2]Journal of Medicinal Chemistry,2012,vol. 55,p. 8236 - 8247,12
[3]Synthetic Communications,2013,vol. 43,p. 2603 - 2614
[4]Journal of Heterocyclic Chemistry,2020,vol. 57,p. 2279 - 2287
[5],2019,vol. 10,p. 1958 - 1965
[6]Patent: WO2006/123145,2006,A1 .Location in patent: Page/Page column 41
[7]Chemical and Pharmaceutical Bulletin,1992,vol. 40,p. 1170 - 1176
[8]Journal of Pharmaceutical Sciences,1982,vol. 71,p. 556 - 561
[9]Chemical and pharmaceutical bulletin,1995,vol. 43,p. 1497 - 1504
[10]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 1291 - 1295
[11]Patent: WO2010/29119,2010,A1 .Location in patent: Page/Page column 63
[12]Journal of Heterocyclic Chemistry,2014,vol. 51,p. 954 - 971
[13]European Journal of Medicinal Chemistry,2015,vol. 99,p. 14 - 35
[14]MedChemComm,2015,vol. 6,p. 1036 - 1042
[15]Chemical Biology and Drug Design,2015,vol. 86,p. 849 - 856
[16]Chemical Communications,2016,vol. 52,p. 5152 - 5155
[17]Phosphorus, Sulfur and Silicon and the Related Elements,2016,vol. 191,p. 1166 - 1173
[18]Organic Letters,2017,vol. 19,p. 2877 - 2880
[19]Organic and Biomolecular Chemistry,2017,vol. 15,p. 8134 - 8139
[20]Tetrahedron Letters,2018,vol. 59,p. 3214 - 3219
[21]Chemical Communications,2018,vol. 54,p. 12182 - 12185
[22]Drug Development Research,2018,vol. 79,p. 406 - 425
[23]Patent: CN109320458,2019,A .Location in patent: Paragraph 0174; 0175; 0176
[24]Organic and Biomolecular Chemistry,2019,vol. 17,p. 3324 - 3327
[25]Organic Letters,2019,vol. 21,p. 6674 - 6678
[26]Journal of Heterocyclic Chemistry,2019,vol. 56,p. 3370 - 3386

13
[ 585-74-0 ]
[ 144660-10-6 ]

Yield	Reaction Conditions	Operation in experiment
96%	With sulfuryl dichloride In neat (no solvent) at 80℃; for 4h;	General procedure for dichlorination of ketones. General procedure: To a 25 mL two necked flask equipped with a condenser and a drying tube was added ketone (5.0 mmol) and sulfuryl chloride (15.0 mmol). The reaction mixture was then stirred at 80 °C. After completion of the reaction (monitored by TLC), the organic mixture was concentrated under reduced pressure to remove the excess amount of sulfuryl chloride, and separated by silica-gel column chromatography using ethyl acetate-hexane as eluent in increasing polarity to yield the desired product.
95%	With sulfuryl dichloride at 80℃;	3 Example 3: Synthesis of α,α-Dichloro-m-methylacetophenone IIc To a 25 mL two-necked flask connected with a drying tube and a reflux condenser, m-methylacetophenone Ic (1.0 mmol) and sulfonyl chloride (3.0 mmol) were added.The reaction mixture was heated to 80°C and stirred for 4-8 hours, and TLC was used to continuously monitor the reaction during the reaction.When the reaction is completed, it is put into a rotary evaporator to remove excess sulfonyl chloride under reduced pressure, and finally directly subjected to silica gel column chromatography (using ethyl acetate-hexane as the eluent) to separate to obtain α,α-dichloro-m-methylacetophenone IIc is a colorless oil with a yield of 95%.
87%	With benzyltrimethylazanium tetrachloro-λ³-iodanuide; acetic acid at 70℃; for 5h;

71.9%	Stage #1: 3-Methylacetophenone With ammonium chloride In acetonitrile for 0.0833333h; Stage #2: With 1,3-dichloro-5,5-dimethylhydantoin In acetonitrile at 40℃; for 16h;	2.4 Synthesis of 2,2-dichloro-1-(pyridin-2-yl)ethan-1-one (10) General procedure: A mixture of NH4Cl (0.14 g, 2.5 mmol), 1-(pyridin-2-yl)ethan-1-one (0.6 g, 5.0 mmol), and 20.0 mL of acetonitrile wasstirred for 5 minutes, then DCDMH (1.95 g, 10 mmol) was added, the mixture was stirred for 16 hours at 40 oC. Aftercompletion of the reaction, solvent was removed and ethyl acetate (20 mL) was added. Then the ethyl acetate was washedtwice with water (20 mL), the organic phase was dried over anhydrous sodium sulfate and subsequently the solvent wasevaporated under reduced pressure. The residues were purified by silica gel column chromatography to give 10 as yellowoil. Yield: 78.7 %.
	Multi-step reaction with 2 steps 1: Reflux 2: hydrogenchloride / acetonitrile; water / 3 h / 20 °C / Electrolysis

Reference： [1]Tu, Dewei; Luo, Juan; Jiang, Wengao; Tang, Qiang [Tetrahedron Letters, 2021, vol. 81]
[2]Current Patent Assignee: CHONGQING MEDICAL UNIVERSITY - CN112961043, 2021, A Location in patent: Page/Page column 5
[3]Kakinami, Takaaki; Urabe, Yasuaki; Hermawan, Irwan; Yamanishi, Hiroko; Okamoto, Tsuyoshi; Kajigaeshi, Shoji [Bulletin of the Chemical Society of Japan, 1992, vol. 65, # 9, p. 2549 - 2551]
[4]Zhang, Shao-Lin; Yang, Zheng; Hu, Xiaohui; Tam, Kin Yip [Bioorganic and Medicinal Chemistry Letters, 2018, vol. 28, # 21, p. 3441 - 3445]
[5]Zhang, Zhenlei; Yang, Jiusi; Wu, Kairui; Yu, Renjie; Bu, Jiping; Huang, Zijun; Li, Shaoke; Ma, Xiantao [Tetrahedron Letters, 2022, vol. 88]

14
[ 585-74-0 ]
[ 96868-61-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With boron tri(hydrogen sulphate) In neat liquid at 100℃; for 7h; Green chemistry;
89%	With trifluorormethanesulfonic acid; oxygen In neat (no solvent) at 120℃; for 12h; Green chemistry; chemoselective reaction;
85%	With toluene-4-sulfonic acid In water at 140℃; for 18h; Neat (no solvent); chemoselective reaction;

82%	With sulfated tungstate In neat (no solvent) at 130℃; for 10h;	3. General experimental procedure for the synthesis of 1,3,5-triarylbenzenes General procedure: In round bottom flask equipped with condenser a mixture of aryl alkyl ketones (3mmol) and sulfated tungstate (20 wt. %) were stirred at 130 C, the progress of the reaction was monitored by TLC. After disapperance of the aryl alkyl ketones and the reaction was continued for additional time of 2 h. The reaction mixture was cooled, diluted with 30 mL of ethyl acetate and filtered to recover the catalyst. The filtrate was washed with 10 mL of water, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel ( 60-120) with (PE:EA=9:1) as eluent to get pure 1,3,5-arylenzenes.
80%	With copper(II) bis(trifluoromethanesulfonate) In toluene at 100℃; for 14h;
78%	With bismuth(III) trifluoromethanesulfonate tetrahydrate In toluene for 4h; Reflux;
76%	With para-dodecylbenzenesulfonic acid In neat (no solvent) at 130℃; for 8h; Green chemistry;	3 General procedure for the synthesis of 1,3,5-triarylbenzenes General procedure: A mixture of acetophenone (3 mmol) and DBSA (0.6 mmol) was heated at 130 °C in a preheated oil bath for 3-8 hours. After completion of the reaction as indicated by thin layer chromatography (TLC), the reaction mixture was cooled to room temperature and diluted with equal volumes of saturated solution of NaHCO3 and brine (5 mL + 5 mL). The resulting solution was extracted with ethyl acetate (10 mL × 3) and the organic layers were combined, dried over anhydrous Na2SO4 and evaporated under reduced pressure to dryness. The crude product obtained was purified by silica gel (60-120 mesh size) column chromatography using 1-2% ethyl acetate in heptane as the eluent to afford the desired products in pure form.
76%	With iodine; 1,2-diamino-benzene In chlorobenzene at 120℃; for 12h; Sealed tube; chemoselective reaction;	General Procedure for synthesis of 4 General procedure: Acetophenone 1 (1mmol), 2-amino aniline 2a (108mg, 1mmol), I2 (13mg, 5mol%), PhCl (3 mL) were added to a reaction tube. The reaction mixture was stirred in a sealed tube at 120 °C for 12 h. The reaction was monitored by TLC. Once the reaction was completed, the reaction mixture was treated with H2O (15.0 mL) and EtOAc (8.0 mL). The organic phase was then separated, and the aqueous phase was extracted with EtOAc (3 x 8 mL). The combined organic phase was dried over Na2SO4, then the solvent was removed under a reduced pressure and the remaining residue was purified by column chromatography.
72%	With phosphomolybdic acid In ethanol for 6.2h; Reflux;
52%	With hydrogenchloride; trimethyl orthoformate In chloroform for 12h;

Reference： [1]Safaei, Hamid Reza; Davoodi, Mansooreh; Shekouhy, Mohsen [Synthetic Communications, 2013, vol. 43, # 16, p. 2178 - 2190]
[2]Zhang, Xu; Wang, Zhiqiang; Xu, Kun; Feng, Yuquan; Zhao, Wei; Xu, Xuefeng; Yan, Yanlei; Yi, Wei [Green Chemistry, 2016, vol. 18, # 8, p. 2313 - 2316]
[3]Zhao, Yanan; Li, Jian; Li, Chunju; Yin, Kun; Ye, Dongyan; Jia, Xueshun [Green Chemistry, 2010, vol. 12, # 8, p. 1370 - 1372]
[4]Wagh, Ganesh D.; Akamanchi, Krishnacharya G. [Tetrahedron Letters, 2017, vol. 58, # 31, p. 3032 - 3036]
[5]Han, Jianwei; Guo, Xin; Liu, Yafeng; Fu, Yajie; Yan, Rulong; Chen, Baohua [Advanced Synthesis and Catalysis, 2017, vol. 359, # 15, p. 2676 - 2681]
[6]Location in patent: scheme or table Ono, Fumiaki; Ishikura, Yuichi; Tada, Yuusuke; Endo, Masato; Sato, Tsuneo [Synlett, 2008, # 15, p. 2365 - 2367]
[7]Prasad, Davinder; Preetam, Amreeta; Nath, Mahendra [Comptes Rendus Chimie, 2013, vol. 16, # 3, p. 252 - 256]
[8]Ding, Yuxin; Ma, Renchao; Ma, Yongmin [Tetrahedron Letters, 2021, vol. 70]
[9]Location in patent: experimental part Phatangare, Kiran; Padalkar, Vikas; Mhatre, Devidas; Patil, Ketan; Chaskar, Atul [Synthetic Communications, 2009, vol. 39, # 22, p. 4117 - 4121]
[10]Sendhoff, Norbert; Kissener, Wolfram; Voegtle, Fritz; Franken, Sybille; Puff, Heinrich [Chemische Berichte, 1988, vol. 121, p. 2179 - 2186]

15
[ 585-74-0 ]
(S)-1-(3-methylphenyl)ethanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With bis(1,5-cyclooctadiene)diiridium(I) dichloride; C₅₃H₇₃FeN₂O₂PS; hydrogen; lithium tert-butoxide In isopropyl alcohol at 25 - 30℃; for 12h; Autoclave; enantioselective reaction;
98%	With (S,S)-RuCl₂(2,2'-bis(di-3,5-xylylphosphino)-1,1'-binaphthyl)(1,1-dianisyl-2-isopropyl-1,2-ethylenediamine); potassium <i>tert</i>-butylate; hydrogen In isopropyl alcohol at 26 - 30℃; for 48h;
98%	With sodium t-butanolate; <i>tert</i>-butyl alcohol; (S)-2,2',6,6'-tetramethoxy-4,4'-bis(di(3,5-xylyl)phosphino)-3,3'-bipyridine In toluene at 20℃; for 14h; enantioselective reaction;

96%	With bis(1,5-cyclooctadiene)diiridium(I) dichloride; (R)-N-(3-methylpyridine-2-methyl)-7-bis-(3,5-di-tert-butylphenyl)phosphino-7′-amino-1,1′-spirodihydroindane; potassium <i>tert</i>-butylate; hydrogen In ethanol at 25 - 30℃; for 0.666667h; Autoclave; optical yield given as %ee; enantioselective reaction;
95%	With bis(1,5-cyclooctadiene)diiridium(I) dichloride; C₃₇H₃₅FeN₂P; hydrogen; potassium carbonate In methanol at 20℃; for 12h; Glovebox; Autoclave; enantioselective reaction;	General procedure for asymmetric hydrogenation of ketones General procedure: In a nitrogen-filled glovebox, a stainless steel autoclave was charged with [Ir(COD)Cl]2(3.4 mg, 0.005 mmol) andL2(6.6 mg, 0.11 mmol) in 1.0 mL of dry MeOH. After stirring for 1h at room temperature, a solution of the substrates1(1.0 mmol) andK2CO3(6.9 mg, 0.05 mmol) in 2.0 mL of MeOH was added to the reaction mixture, and then the hydrogenation was performed at room temperature under an H2pressure of 20 bar for 12 h. The solvent was then evaporated and the residue was purified by flash column chromatography to give the corresponding hydrogenation product which was analyzed by chiral HPLC to determine the enantiomeric excesses.
93%	With triiron dodecarbonyl; C₅₂H₅₈N₄P₂; hydrogen; potassium hydroxide In methanol at 45℃; for 10h; enantioselective reaction;
92%	With AMBERLITE XAD-7; Geotrichum candidum IFO 4597 In water at 30℃; for 24h;
91%	Stage #1: With (p-cymene)ruthenium(II) chloride; triethylamine; N-[(1S,2S)-2-amino-1,2-diphenylethyl]-4-methylbenzenesulfonamide In dichloromethane at 35℃; for 1h; Stage #2: 3-Methylacetophenone With tetra-(n-butyl)ammonium iodide In water; sodium formate at 40℃; for 4.5h; Ultrasonic irradiation; optical yield given as %ee;
83%	With 2-(N-morpholino)ethanesulfonic acidbuffer; NAD; isopropyl alcohol at 30℃; for 20h; acetone powder of Geotrichum candidum;
82%	With 7,7’-dicyclohexyl VANOL; trimethylaluminum; isopropyl alcohol In pentane at -10℃; for 24h; Molecular sieve; enantioselective reaction;
75%	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; isopropyl alcohol at 20℃; for 3h; enantioselective reaction;
60%	With n-hexan-2-ol In hexane; water at 30℃; for 24h; immobilized Geotrichum candidum;
60%	With C₂₃H₃₁ClN₂O₂RuS; potassium hydroxide In isopropyl alcohol at 24 - 25℃; for 24h;
43%	With n-hexan-2-ol; Geotrichum candidum IFO 4597 cells on BL-100 polymer In hexane at 30℃; for 24h;
31%	With Synechococcus sp. PCC 7942 at 20℃; for 72h; Irradiation;
18%	With glucose dehydrogenase; D-glucose; ketoreductase from Pichia glucozyma; nicotinamide adenine dinucleotide phosphate In aq. buffer at 30℃; Enzymatic reaction; enantioselective reaction;
	With (R)-1-[(1R,4R,5R,6S)-5,6-Me₂CO₂-2-aza-3-norbornyl]ethanol; potassium isopropoxide; isopropyl alcohol at 20℃; for 0.0666667h;
	With sodium isopropylate; isopropyl alcohol; Boc-L-alanine(2S)-hydroxypropylamide at 20℃; for 1h;
	With D-glucose; D-glucose dehydrogense; Pyrococcus furiosus alcohol dehydrogenase In dimethyl sulfoxide at 37℃;
	With chiral dipyridylphosphine Ru; potassium <i>tert</i>-butylate; hydrogen In isopropyl alcohol; <i>tert</i>-butyl alcohol at 20℃; for 50h;
	With D-glucose; D-glucose dehydrogenase; NADPH In dimethyl sulfoxide at 20℃;
87 % ee	Stage #1: 3-Methylacetophenone With phenylsilane In toluene at -20℃; for 12h; Stage #2: With hydrogenchloride In water; toluene	Reaction conditions: 100 mg-42 g substrate, substrate concentration = 0.6-1 M toluene, >99% conversion is observed in all cases.
	With C₅₅H₆₉ClFeN₂O₂P₂Ru; potassium <i>tert</i>-butylate; hydrogen In methanol; ethanol at 40℃; for 0.333333h;
	With [RhCl₂(p-cymene)]2; FTsDPEN; sodium formate; tetra-(n-butyl)ammonium iodide; triethylamine In dichloromethane; water at 40℃; for 3h; Inert atmosphere; optical yield given as %ee;
	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; lithium chloride; sodium t-butanolate; Boc-L-alanine(2S)-hydroxypropylamide In tetrahydrofuran; ethanol; water at 40℃; for 3h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	General procedure for the ATH of aryl alkyl ketones General procedure: To a 10 ml vial equipped with a septum and stirring bar, [Ru(p-cymene)Cl2)2 (0.0024 g, 0.004 mmol), ligand 1 (0.0028 g, 0.0088 mmol), and LiCl (0.0034 g, 0.08 mmol) were added. The vial was sealed and the atmosphere exchanged via 3 × vacuum/N2 cycles. The vial was placed in an oil bath at 40 °C and dry THF (0.8 ml), 99% EtOH (0.4 ml) and the substrate (0.8 mmol) were added. The mixture was allowed to stir for 20 min, after which NaOtBu (0.0046 g, 0.048 mmol) dissolved in 99% EtOH (0.4 ml) was added. Aliquots were removed and filtered through a small plug of silica before analysis on chiral GC. Solid substrates were added to the vial at the same time as the metal precursor and the ligand.
	With RuCl₂(1,1'-bis(diphenyphosphino)ferrocene)[(1S,1'S)-6,6'-dibromo-1,1'-biisoindoline]; potassium <i>tert</i>-butylate; hydrogen In propan-1-ol at 20℃; for 30h; Inert atmosphere; Autoclave; optical yield given as %ee; enantioselective reaction;
	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; C₂₇H₄₂N₂O₈; sodium isopropylate; isopropyl alcohol; lithium chloride In tetrahydrofuran at 20℃; for 3h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
92 % ee	With RuCl2(PPh3)2{(1S,1’S)-1,1’-biisoindoline}; potassium <i>tert</i>-butylate; hydrogen; triphenylphosphine In isopropyl alcohol at 20℃; for 36h; Autoclave; enantioselective reaction;
	With enzymes from carrot (Daucus carota) roots Enzymatic reaction;
97 % ee	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; C₂₆H₂₉N₄O₃S⁽¹⁺⁾*Cl^(1-); sodium formate In water at 20℃; for 25h; enantioselective reaction;	2.7 General procedure for asymmetric transfer hydrogenation General procedure: To a solution of ligand 5d (2.1 mg, 0.004 mmol) in water (1 mL) was added [Cp*RhCl2]2 (1.2 mg, 0.002 mmol), HCO2Na (41 mg, 3.0 mmol), and ketone (2.0 mmol). The reaction mixture was stirred at room temperature for the time as indicated in Tables 1 and 2 . The reaction mixture was extracted by ethyl ether. The conversion was determined by 1H NMR analysis of the crude product. After concentration, the crude product was purified by chromatography on silica gel to give the pure product.
97 % ee	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; C₂₆H₂₉N₄O₃S⁽¹⁺⁾*Cl^(1-); sodium formate In water at 20℃; for 25h; Green chemistry; enantioselective reaction;	2.7 General procedure for asymmetric transfer hydrogenation General procedure: To a solution of ligand 5d (2.1 mg, 0.004 mmol) in water (1 mL) was added [Cp*RhCl2]2 (1.2 mg, 0.002 mmol), HCO2Na (41 mg, 3.0 mmol), and ketone (2.0 mmol). The reaction mixture was stirred at room temperature for the time as indicated in Tables 1 and 2. The reaction mixture was extracted by ethyl ether. The conversion was determined by 1H NMR analysis of the crude product. After concentration, the crude product was purified by chromatography on silica gel to give the pure product.
91 % ee	With [Ru-Cl(bis(2-diphenylphosphanylphenyl)methanone)((R,R)-DPEN)]Cl; potassium <i>tert</i>-butylate; hydrogen In ethanol at 25℃; for 4h; Autoclave; enantioselective reaction;
>99% ee	With glucose; glucose dehydrogenase from Bacillus subtilis CGMCC 1.1398; medium-chain dehydrogenase from Kuraishia capsulate CBS₁₉₉₃; NAD In aq. phosphate buffer for 16h; Enzymatic reaction; enantioselective reaction;	Substrate scope and enantioselectivity determination General procedure: Substrate scope and enantioselectivity determination The relative activities of 26 substrates were measured using thepreviously described assay protocol with adjusted ratio of enzymeand substrate concentration. The a-chloroacetophenone activitywas assumed 100%.Enantioselectivity was determined by examining the reductionof aromatic ketones using an NADH-regeneration system consist-ing of the puried KcDH and glucose dehydrogenase (GDH) fromBacillus subtilis CGMCC 1.1398. The 1-mL reaction mixture con-tained 0.5 mM NAD+, 10 mM ketone, 1 U KcDH, 50 mg glucoseand 2 U GDH in 50 mM potassium phosphate buffer (pH 7.0). After16 h, the reaction sample was equally separated into two parts,with one terminated by adding an equal volume of methanol, fol-lowed by HPLC analysis to determine the conversion ratio, and theother extracted with ethyl acetate, followed by ee analysis. Meth-ods used for analysing chiral products using HPLC or GC aredescribed in Supplementary Table S1.
91 % ee	With water; sodium acetate at 39.84℃; for 1.5h; enantioselective reaction;
> 99 % ee	With halophilic alcohol dehydrogenase ADH₂ from Haloferax volcanii; NADPH In ethanol; acetonitrile at 25℃; Enzymatic reaction; enantioselective reaction;
93 %Chromat.	With C₅₀H₄₇Cl₂N₆O₅PRuS₂; potassium isopropoxide; isopropyl alcohol at 28℃; for 0.166667h; Inert atmosphere; enantioselective reaction;
99 %Chromat.	With (S)-selective alcohol dehydrogenase whole-cell lyophilisate In aq. buffer enantioselective reaction;
90 % ee	With hydrogen; C₃₂H₁₂BF₂₄^(1-)*C₃₉H₄₃IrN₂P⁽¹⁺⁾ In isopropyl alcohol at 20℃; for 0.5h; enantioselective reaction;
	With pyridoxal 5'-phosphate; NAD; alcohol dehydrogenase from Candida parapsilosis-W₂₈₆A mutant; Bacillus megaterium ω-transaminase; diisopropylamine In aq. acetate buffer at 30℃; for 24h; Green chemistry; Enzymatic reaction;
	Multi-step reaction with 3 steps 1: sodium tetrahydroborate; methanol / 0.67 h / 0 - 20 °C / Inert atmosphere 2: (OC-6-23)-[2-[6-[(amino-κN)methyl]-2-pyridinyl-κN]-5-methylphenyl-κC][1,1'-(1,4-butanediyl)bis[1,1-diphenylphosphine-κP]]chlororuthenium(II); copper(l) chloride; sodium t-butanolate; (R,R)-1,2-bis(2,5-diphenylphospholanyl)ethane / toluene / 14 h / 20 °C / Glovebox; Inert atmosphere 3: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C / Inert atmosphere
90 % ee	With sodium formate at 40℃; for 18h; enantioselective reaction;
> 99 % ee	With pyridoxal-5-phosphate; tris hydrochloride; diisopropylamine at 30℃; for 24h; Enzymatic reaction; enantioselective reaction;

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[2]Ohkuma; Koizumi; Doucet; Pham; Kozawa; Murata; Katayama; Yokozawa; Ikariya; Noyori [Journal of the American Chemical Society, 1998, vol. 120, # 51, p. 13529 - 13530]
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[5]Qin, Chao; Hou, Chuan-Jin; Liu, Hongzhu; Liu, Yan-Jun; Huang, De-Zhi; Hu, Xiang-Ping [Tetrahedron Letters, 2018, vol. 59, # 8, p. 719 - 722]
[6]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]
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[10]Guan, Yong; Mohammadlou, Aliakbar; Staples, Richard; Sullivan, Ryan P.; Wulff, William D.; Yin, Xiaopeng; Zheng, Li [ACS Catalysis, 2020, vol. 10, # 13, p. 7188 - 7194]
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16
[ 585-74-0 ]
[ 70138-19-1 ]

Yield	Reaction Conditions	Operation in experiment
80%		General procedure: A mixture of 1-(4-(trifluoromethyl)phenyl)ethanone (400 mg, 2.13 mmol), Ti(O-i-Pr)4 (1.25 mL, ?4.25 mmol) and ammonia in EtOH (2 M, 5.30 mL, ?10.6 mmol) was stirred under argon at room temperature for 24 h NaBH4 (120 mg, 3.19 mmol) was then added, and the resulting mixture was stirred for another 24 h. The pH of the reaction mixture was adjusted to pH 2 using HCl (6 M), and washed with tert-butyl methyl ether (TBME) (3 × 20 mL). Using NaOH (pellets) the pH was adjusted to ca 10, and the mixture was extracted with TBME (6 × 30 mL). The combined organic phase was dried over MgSO4, and the solvent was removed under reduced pressure to give 210 mg (1.11 mmol, 52%) of a yellow oil.
	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; ammonium formate; In methanol; at 70℃; for 7h;Inert atmosphere;	General procedure: The corresponding ketone (20 mmol, 1.0 eq) and CH3OH (20 mL) were added to a 250 mL Schlenk tube containing [RhCp*Cl2]2 (61.8 mg, 100 mumol, 0.005 equiv) and HCOONH4 (6.36 g, 100 mmol, 5.0eq). The brown mixture was frozen, and the whole system was evacuated. The system was closed and then stirred at 70 C for 7 h. After the dark green resulting solution was cooled to room temperature, 1M aqueous HCl solution (38.4 mL) was added, and the mixture was washed twice with CH2Cl2 (5 mL) to remove the neutral compounds. After addition of a cold 12 M aqueous NaOH solution (3.6 mL) to the aqueous layer, the mixture was extracted six times with CH2Cl2 (12 mL). The combined organic layers were dried over anhydrous Na2SO4. Filtration and evaporation under reduced pressure gave crude amine,which was used without purification. All the crude corresponding amine was dissolved in dichloromethane (50 mL), and TCCA (trichloroisocyanuric acid) (3.2 g, 14 mmol) was added in a250 ml round-bottom flask at 0 C. Then, the mixture was stirred at ambient temperature during 1 h. Triethylamine (6.0 g, 6 mol) dissolved in dichloromethane (50 mL) was added, and the resulting mixture was washed with water (200 mL) and hydrochloric acid (1 M, 200 mL)successively. The organic layer was dried over anhydrous sodium sulfate. After concentration under reduced pressure, purification by column chromatography on silica gel (n-hexane/EtOAc:40/1) afforded pure product.

Reference： [1]Chemical Science,2020,vol. 11,p. 2973 - 2981
[2]European Journal of Medicinal Chemistry,2011,vol. 46,p. 6002 - 6014
[3]Advanced Synthesis and Catalysis,2016,vol. 358,p. 358 - 363
[4]Chirality,2018,vol. 30,p. 900 - 906
[5]Bulletin des Societes Chimiques Belges,1963,vol. 72,p. 202 - 207
[6]Collection of Czechoslovak Chemical Communications,1973,vol. 38,p. 441 - 446
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[10]Organic Letters,2019,vol. 21,p. 6860 - 6863
[11]Tetrahedron Letters,2020
[12]ChemSusChem,2020,vol. 13,p. 3110 - 3114

17
[ 383-63-1 ]
[ 585-74-0 ]
[ 53764-99-1 ]

Reference： [1]Organic and Biomolecular Chemistry,2016,vol. 14,p. 1531 - 1535
[2]Journal of Medicinal Chemistry,1997,vol. 40,p. 1347 - 1365
[3]Bioorganic and Medicinal Chemistry Letters,2004,vol. 14,p. 499 - 504
[4]Bioorganic and Medicinal Chemistry,2018,vol. 26,p. 3406 - 3413

18
[ 585-74-0 ]
[ 1445-91-6 ]

Yield	Reaction Conditions	Operation in experiment
98%	With [((R,R)-diphenylethylenediamine)((R)-Binap)dichlororuthenium(II)]; potassium <i>tert</i>-butylate; hydrogen In isopropyl alcohol at 26 - 30℃; for 2h;

Reference： [1]Ohkuma; Koizumi; Doucet; Pham; Kozawa; Murata; Katayama; Yokozawa; Ikariya; Noyori [Journal of the American Chemical Society, 1998, vol. 120, # 51, p. 13529 - 13530]

19
[ 7287-81-2 ]
(R)-(+)-1-(3-methylphenyl)-1-ethanol [ No CAS ]
[ 585-74-0 ]

Reference： [1]Angewandte Chemie - International Edition,2014,vol. 53,p. 3178 - 3182
Angew. Chem.,2014,vol. 126,p. 3242 - 3246,5
[2]Journal of the Chemical Society. Perkin transactions I,1999,p. 2397 - 2402
[3]Journal of Organic Chemistry,2003,vol. 68,p. 402 - 406
[4]Journal of Organic Chemistry,2003,vol. 68,p. 402 - 406
[5]Organic and Biomolecular Chemistry,2012,vol. 10,p. 2730 - 2732
[6]Tetrahedron Letters,2016,vol. 57,p. 4563 - 4567

20
[ 23040-54-2 ]
[ 585-74-0 ]

Yield	Reaction Conditions	Operation in experiment
95%	With magnesium hydrogen sulfate; water; silica gel In hexane for 0.5h; Heating;
95%	With diphenyl ditelluride; oxygen In acetonitrile for 24h; Irradiation;	General procedure for the oxidative deoximation reactions in solvents General procedure: To a 20 mL test tube, 0.5 mmol of ketoximes (1), 0.005 mmol of (PhTe)2 and 1 mL solvent (EtOAc or MeCN) were added. The tube was then equipped with an O2 balloon and was irradiated by the LEDs blue light for 24 h. The mixture was separated by column chromatography (eluent: petroleum/EtOAc = 15/1) to produce the related ketones (2).
91%	With ferrous(II) sulfate heptahydrate; benzyl seleninic acid In ethyl acetate at 60℃; for 24h; Green chemistry;

82%	With silica chromate; silica gel for 0.0333333h; microwave irradiation;
60%	With oxygen; pivalaldehyde In fluorobenzene at 20℃; for 4h;
58%	With dibenzyl diselenide; dihydrogen peroxide In acetonitrile at 60℃; for 24h;

Reference： [1]Shirini; Zolfigol; Mallakpour; Mallakpour; Hajipour; Baltork [Tetrahedron Letters, 2002, vol. 43, # 8, p. 1555 - 1556]
[2]Deng, Xin; Qian, Rongrong; Zhou, Hongwei; Yu, Lei [Chinese Chemical Letters, 2021, vol. 32, # 3, p. 1029 - 1032]
[3]Chen, Chao; Zhang, Xu; Cao, Hongen; Wang, Fang; Yu, Lei; Xu, Qing [Advanced Synthesis and Catalysis, 2019, vol. 361, # 3, p. 603 - 610]
[4]Zolfigol, Mohammad Ali; Khazaei, Ardeshir; Ghorbani-Choghamarani, Arash; Rostami, Amin [Phosphorus, Sulfur and Silicon and the Related Elements, 2006, vol. 181, # 11, p. 2453 - 2458]
[5]Blay, Gonzalo; Benach, Elisabeth; Fernández, Isabel; Galletero, Sales; Pedro, José R.; Ruiz, Rafael [Synthesis, 2000, # 3, p. 403 - 406]
[6]Jing, Xiaobi; Yuan, Dandan; Yu, Lei [Advanced Synthesis and Catalysis, 2017, vol. 359, # 7, p. 1194 - 1201]

21
[ 585-74-0 ]
(1R)-1-(3-methylphenyl)ethan-1-amine [ No CAS ]
[ 138457-18-8 ]

Reference： [1]Angewandte Chemie - International Edition,2003,vol. 42,p. 5472 - 5474
[2]Journal of the Chemical Society. Perkin Transactions 2 (2001),2000,p. 1339 - 1347
[3]Organic and biomolecular chemistry,2012,vol. 10,p. 8960 - 8962,3

22
[ 585-74-0 ]
[ 75369-41-4 ]

Yield	Reaction Conditions	Operation in experiment
85.3%	With NBS; azobisisobutyronitrile In Carbon tetrachloride at 90℃; for 6h; Inert atmosphere;	18.1 (1) Preparation of compound 18-2 At nitrogen atmosphere, at room temperature to 1-(m-tolyl)ethyl-1-one 18-1 (2.5 g, 18.68 mmol) in CCl NBS (3.64g, 20.50mmol) and AIBN (0.306g, 1.868mmol) were added to the mixture in 4 (20 mL). The reaction mixture was stirred at 90 °C for 6 h under a nitrogen atmosphere. The reaction mixture was concentrated to give a crude compound, which was purified by column chromatography (PE / EA = 0-5%), to give 1- (3- (bromomethyl)phenyl) ethyl-1-one 18-2 (3.386g, 85.3%).
70%	With NBS; azobisisobutyronitrile In acetonitrile at 90℃; for 6h; Inert atmosphere;	2.A 1-(3-Bromomethyl-phenyl)-ethanone (2-2A). To a stirred solution of 1-m-tolylethanone 2-1 A (25 g, 186.43 mmol) in ACN (ACN; 200 mL) was added NBS (36.4 g, 205.07 mmol) and azoisobutyronitrile (AIBN; 3.06 g, 18.64 mmol) at room temperature (ambient; RT). The reaction mixture was warmed to 90 °C for 6 hours (hr) under N2 atmosphere. The reaction mixture solvent was evaporated under reduced pressure and the crude residue washed with toluene (500 mL) and filtered the precipitate (NBS). Filtrate evaporated under reduced pressure and the crude residue was purified by flash column chromatography (100-200 silica) using 3% EtOAc (EtOAc) in petroleum ether (pet. ether) to afford 2-2A (27.6 g, 129.57 mmol, 70% yield) as an off-white solid. MS (ESI): m/z 213.0 (M+l)+.
69%	With NBS; dibenzoyl peroxide In acetonitrile at 80℃; for 6h;	5 A solution of 1-M-TOLYL-ETHANONE (5. 0 g, 37. 3 mmol) in anh. MECN (45 mL) was treated WITH N-BROMOSUCCINIMIDE (6. 63 g, 37. 3 mmol) and benzoyl peroxide (9. 02 g, 37. 3 MMOL). The reaction mixture was heated at 80 °C for 6 h. On cooling, the mixture was concentrated and the resulting syrup was dissolved in ET20 and treated with NAHCO3. The ethereal layer was washed with brine and dried on MGSO4. The solvent was evaporated and the resulting residue was purified by Si02 gel chromatography (heptane/EtOAc 12 : 1- 3 : 1) to afford 1- (3-bromomethyl-phenyl)-ethanone (5. 5 g, 69 %). 1H-NE (CDC13) : W2. 54 (s, 3H, CH3), 4. 45 (s, 2H, CH2), 7. 38 (t, 1H, J= 8. 0 Hz, Ph-H), 7. 52 (d, 1H, J= 8. 0 Hz, Ph- H), 7. 81 (d, 1H, J= 8. 0 Hz, Ph-H), 7. 90 (s, 1H, Ph-H). 1H-Imidazole (0. 15 g, 2. 25 mmol) in anh. DMF (8 mL) was cooled on an ice bath and treated with Cs2CO3 (0. 67 g, 2. 07 mmol). After stirring for 30 min 1- (3-BROMOMETHYL- phenyl)-ethanone (0. 4 g, 1. 88 mmol) was added. The reaction mixture was warmed to room temperature and was stirred for 20 h. Ice water was added and the mixture was extracted with ET20. The combined extracts were washed with brine and dried on MgSO4. The solvent was evaporated and the residue was purified by SI02 gel chromatography using heptane/EtOAc (12 : 1-3 : 1) to afford 1-(3-IMIDAZOL-1-YLMETHYL-PHENYL)-ETHANONE (0. 23 g, 60 %) as a brown SYRUP. IH-NMR (CDC13) D : 2. 57 (s, 3H, CH3), 5. 16 (s, 2H, CH2), 6. 89 (s, 1H, imidazole-H), 7. 08 (s, 1H, imidazole-H), 7. 30 (d, 1H, J= 8. 0 Hz, Ph-H), 7. 45 (t, 1H, J= 8. 0 Hz, Ph-H), 7. 54 (s, 1H, imidazole-H), 7. 77 (s, 1H, Ph-H), 7. 89 (d, 1H, J= 8. 0 Hz, Ph-H). An aliquot of this material (0. 10 g, 0. 50 MMOL) was treated with N, N-dimethyl formamide dimethylacetal (1 mL, 8. 39 mmol) at 100 °C for 7 h. On cooling, the reaction mixture was concentrated and the resulting residue was purified by SI02 chromatography using heptane/EtOAc (3 : 1-1 : 10) to afford 3-DIMETHYLAMINO-1- (3-IMIDAZOL-1-YLMETHYL-PHENYL)- propenone as yellow solid (0. 11 g, 83 %). 1H-NMR (CDCL3) No.. 2. 88 (s, 3H, CH3), 3. 11 (s, 3H, CH3), 5. 12 (s, 2H, CH2), 5. 61 (d, 1H, J = 12. 0 Hz, CH), 6. 88 (s, 1H, imidazole-H), 7. 04 (s, 1H, imidazole-H), 7. 15 (d, 1H, J= 6. 0 Hz, Ph-H), 7. 35 (t, 1H, J= 7. 5 Hz, Ph-H), 7. 54 (s, 1H, imidazole-H), 7. 71 (s, 1H, Ph-H), 7. 75 (m, 2H, Ph-H and CH). A mixture of the latter compound (0. 10 g, 0. 39 mmol), 3-nitro-phenyl guanidine nitrate (0. 11 g, 0. 43 mmol), and NAOH (0. 019 g, 0. 47 mmol) in 2-methoxylethanol (4 mL) was heated at 125 °C for 20 h. The solvent was evaporated and the residue was purified by Si02 gel chromatography using EtOAc and ETOAC/MEOH (10 : 1) to afford the title compound as a yellow solid (0. 079 g, 55 %). Anal. RP-HPLC : tR = 17 min (0-60 % MECN, purity > 95 %). 1H-NMR (DMSO-D6) : A 5. 32 (s, 2H, CH2), 6. 91 (s, 1H, imidazole-H), 7. 23 (s, 1H, imidazole-H), 7. 41 (d, 1H, J=8. 0 Hz, Ph-H), 7. 51 (d, J= 5. 5 Hz, pyrimidine-H), 7. 54 (t, 1H, J= 8. 0 Hz, Ph-H), 7. 59 (t, 1H, J= 8. 0 Hz, Ph-H), 7. 81 (m, 2H, Ph-H), 8. 05 (d, 1H, J= 8. 0 Hz, Ph-H), 8. 14 (d, 1H, J= 8. 0 Hz, Ph-H), 8. 18 (s, 1H, Ph-H), 8. 65 (d, 1H, J= 5. 5 Hz, pyrimidine-H), 9. 14 (s, 1H, imidazole-H), 10. 27 (s, 1H, NH). I3C-NMR (DMSO-D6) : No. 60. 4, 109. 8, 113. 1, 116. 3, 120. 3, 125. 3, 126. 8, 127. 2, 129. 5, 130. 1, 130. 5, 130. 6, 137. 5, 138. 1, 139. 4, 142. 6, 148. 9, 160. 2, 160. 4, 163. 9. MS (EST) M/Z 373. 2 [M+H] +, CZOHL6N602 requires 372. 38.

60%	With NBS; dibenzoyl peroxide In Carbon tetrachloride for 12h; Reflux;
58%	With NBS; benzoic peroxyanhydride In acetonitrile at 85℃; Inert atmosphere;	1-[3-(bromomethyl)phenyl]ethan-1-one A solution of meta-tolylethanone (5 g, 37 mmol), N-bromosuccinimide (1 eq, 6.6 g, 37 mmol) and benzoic peroxyanhydride (0.2 eq, 1.8 g, 7.5 mmol) in acetonitrile was stirred at 85° C under argon overnight. The solvent was removed under reduced pressure. The residue was purified by FCC (EtOAc in Hexane 0-5 %) to give the desired product as a yellow oil.Y = 58 %MS ES+: not ionised1H NMR (400 MHz, Chloroform-d) δ 8.00 (t, J = 2 Hz, 1H), 7.94 - 7.88 (m, 1H), 7.65 - 7.59 (m, 1H), 7.48 (t, J = 8 Hz, 1H), 4.56 (s, 2H), 2.64 (s, 3H).
38.8%	With NBS; dibenzoyl peroxide In Carbon tetrachloride	R.1 Production of 3'-Bromomethylacetophenone Referential Example 1 Production of 3'-Bromomethylacetophenone 3'-Methylacetophenone (5.00 g; 37.3 mmol), N-bromosuccinimide (6.63 g; 37.3 mmol), and benzoyl peroxide (100 mg) were added to carbon tetrachloride (70 ml), and the mixture was refluxed for 1 hour. The mixture was left to cool to room temperature, and crystals that precipitated were removed by filtration. The filtrate was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=20:1), to thereby yield 3.08 g of the target compound (yield: 38.8%). 1H-NMR (CDCl3, ppm); 2.62 (3H, s), 4.53 (2H, s), 7.46 (1H, t, J=7.83 Hz), 7.62 (1H, dt, J=7.83 Hz, (16.2 Hz), 7.89 (1H, dt, J=7.83 Hz, 1.62 Hz), 7.97 (1H, t, J=1.62 Hz).
	With NBS In Carbon tetrachloride Irradiation;
	With NBS; dibenzoyl peroxide In Carbon tetrachloride Heating;
	With NBS In Carbon tetrachloride for 5h; Reflux;	1 m-Methylacetophenone (10.0 g, 74.5 mmol), iV-bromosuccinimide (13.93 g, 78.3 mmol) and dibenzoylperoxide (8 mg) were dissolved in carbon tetrachloride (70 mL) and the mixture was heated in reflux for 5 h, cooled to RT and filtered. The filtrate was concentrated and purified on silica gel (petroleum ether, bp 40-60 0C / ethyl acetate, 10:1, v/v). Yield was 12.9 g. 1H NMR (CDCl3) ? 7.92 (IH, s); 7.89 (IH, d, J 7.8); 7.60 (IH, d, J 7.8); 7.46 (IH, t, J 7.8); 4.53 (2H, s); 2.62 (3H, s).
	With NBS; dibenzoyl peroxide In acetonitrile at 85℃; for 20h; Inert atmosphere;	28.1 Example 28; N-(4-(3-((dimethylamino)methyl)phenyl)-5-(2-(trifluoromethyl)phenoxy)thiazol-2-yl)-2-(4- (ethylsulfonyl)phenyl)acetamide trifluoroacetate; Step 1:; A solution of l-m-tolylethanone (5.0 g), NBS (6.63 g) and benzoic peroxyanhydride (1.81 g) in acetonitrile (10 mL) was stirred at 85 °C under nitrogen for 20 hours. Solvent was removed, and the residue was purified by flash chromategraphy (EtOAc : PE = 0: 1 to 1:20) to give 1- (3-(bromomethyl)phenyl)ethanone (2.4 g) as an oil. MS(ES+) m/z 213 (MH4).
	With NBS; dibenzoyl peroxide In Carbon tetrachloride for 3h; Reflux;	General procedure for the synthesis of compounds 1-15 The solution of 3-methylacetophenone (1 mmole) in 10 ml CCl4 was refluxed with N-bromosuccinamide(1 mmole) in presence of catalytic amount of benzoyl peroxide for 2-3 h. The reaction was monitored by TLC. The reaction mixture was filtered and concentrated under vacuum to yield 1-(3-(bromomethyl)phenyl)ethanone 1 as yellow oil, which was used for next reaction without further purification.
	With NBS; dibenzoyl peroxide In lithium hydroxide monohydrate; 1,2-dichloro-benzene at 140℃; for 16h;
	With NBS; azobisisobutyronitrile In chloroform at 80℃; for 2h;

Reference： [1]Current Patent Assignee: HUADONG MEDICINE CO., LTD. - WO2022/78152, 2022, A1 Location in patent: Page/Page column 76-77
[2]Current Patent Assignee: COCRYSTAL PHARMA, INC. - WO2016/154241, 2016, A1 Location in patent: Paragraph 231; 232
[3]Current Patent Assignee: CYCLACEL PHARMACEUTICALS, INC. - WO2005/12262, 2005, A1 Location in patent: Page/Page column 47-48
[4]Location in patent: experimental part Ranaweera, Ranaweera A. A. Upul; Zhao, Yu; Muthukrishnan, Sivaramakrishnan; Keller, Christopher; Gudmundsdottir, Anna D. [Australian Journal of Chemistry, 2010, vol. 63, # 12, p. 1645 - 1655]
[5]Current Patent Assignee: NODTHERA LTD - WO2018/167468, 2018, A1 Location in patent: Page/Page column 51; 52
[6]Current Patent Assignee: POLA ORBIS HOLDINGS INC - US6586633, 2003, B1
[7]Conway, Stuart J; Miller, Jacqueline C; Howson, Patrick A; Clark, Barry P; Jane, David E [Bioorganic and Medicinal Chemistry Letters, 2001, vol. 11, # 6, p. 777 - 780]
[8]Zhang, Xuechun; Pais, Godwin C.G.; Svarovskaia, Evguenia S.; Marchand, Christophe; Johnson, Allison A.; Karki, Rajeshri G.; Nicklaus, Marc C.; Pathak, Vinay K.; Pommier, Yves; Burke Jr., Terrence R. [Bioorganic and Medicinal Chemistry Letters, 2003, vol. 13, # 6, p. 1215 - 1219]
[9]Current Patent Assignee: PERKINELMER INC - WO2009/115644, 2009, A1 Location in patent: Page/Page column 10; 17
[10]Current Patent Assignee: GLAXOSMITHKLINE PLC - WO2012/100734, 2012, A1 Location in patent: Page/Page column 38
[11]Bag, Seema; Ghosh, Sanjukta; Tulsan, Rekha; Sood, Abha; Zhou, Weihong; Schifone, Christine; Foster, Michelle; Levine III, Harry; Török, Béla; Török, Marianna [Bioorganic and Medicinal Chemistry Letters, 2013, vol. 23, # 9, p. 2614 - 2618]
[12]Baragana, Beatriz; Norcross, Neil R.; Wilson, Caroline; Porzelle, Achim; Hallyburton, Irene; Grimaldi, Raffaella; Osuna-Cabello, Maria; Norval, Suzanne; Riley, Jennifer; Stojanovski, Laste; Simeons, Frederick R. C.; Wyatt, Paul G.; Delves, Michael J.; Meister, Stephan; Duffy, Sandra; Avery, Vicky M.; Winzeler, Elizabeth A.; Sinden, Robert E.; Wittlin, Sergio; Frearson, Julie A.; Gray, David W.; Fairlamb, Alan H.; Waterson, David; Campbell, Simon F.; Willis, Paul; Read, Kevin D.; Gilbert, Ian H. [Journal of Medicinal Chemistry, 2016, vol. 59, # 21, p. 9672 - 9685]
[13]Current Patent Assignee: AGIOS PHARMACEUTICALS INC; PHARMARESOURCES SHANGHAI CO LTD - WO2019/35863, 2019, A1 Location in patent: Page/Page column 4

23
[ 17933-03-8 ]
[ 108-24-7 ]
[ 585-74-0 ]

Yield	Reaction Conditions	Operation in experiment
76%	With 2C₆₀H₈₀NaO₁₂⁽²⁺⁾*Cl₆Pd₂^(2-); potassium hydrogencarbonate; triphenylphosphine In toluene at 110℃; for 3h; Inert atmosphere;	General procedure for the acylodeboronation reaction of arylboronic acids with aceticanhydride. General procedure: A 5 mL flask charged with acetic anhydride (1.0 mmol), arylboronic acid (0.5mmol), KHCO3 (1.0 mmol), complex 1 (0.5 mol%, 3.1 mg), PPh3 (0.01 mmol, 1.3 mg) andtoluene (2.0 mL) was evacuated and backfilled with N2 for three times before the reaction wasput into a preheated 110 oC oil bath. After the reaction was finished in 3h, the reaction mixture was cooled to room temperature, filtered through a short silica column and washed with ethylacetate. Then the combined filtrates were concentrated in vacuo and the residue was purified byflash chromatography (eluent: ethylacetate/petroleum ether). All the products were knowncompounds and characterized by comparing mp, 1H NMR and 13C NMR spectra with literature.
68%	In 1,4-dioxane for 16h; Heating;

Reference： [1]Zhang, Jinli; Han, Zixing; Li, Junmiao; Wu, Yangjie [ARKIVOC, 2013, vol. 2013, # 4, p. 251 - 271]
[2]Frost; Wadsworth [Chemical Communications, 2001, # 22, p. 2316 - 2317]

24
[ 100-51-6 ]
[ 585-74-0 ]
[ 54095-43-1 ]

Yield	Reaction Conditions	Operation in experiment
90%	With lithium tert-butylate In toluene at 110℃; for 12h; Inert atmosphere;
88%	With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H₂O); Cs₂CO₃ In tert-Amyl alcohol for 6h; Reflux;
83%	With bis(μ-chloro)-bis[1,3-di(2-pyridyl)-4,6-dimethylbenzene-N,C(2'),N-iridium chloride]; Cs₂CO₃ In tert-Amyl alcohol for 12h; Reflux;

83%	With Mn(7-hydroxy-2-methyl-1,8-naphthyridine-N-oxide)(CO)<SUB>3</SUB>Br; potassium hydroxide In toluene at 130℃; for 0.75h; Sealed tube;
81%	With C₃₈H₄₃IrN₂PS₂⁽¹⁺⁾*CF₃O₃S^(1-); Cs₂CO₃ In tert-Amyl alcohol at 120℃; for 24h; Schlenk technique; Inert atmosphere;	Typicalprocedure for the synthesis of 5a General procedure: Catalyst 2b (1 mol%, 0.01 mmol), benzylalcohol (1.1 mmol), acetophenone (1.0 mmol), Cesiumcarbonate (1.0 mmol), and tert-amyl alcohol (2 mL) was added toa Schlenk tube under N2 atmosphere. The mixture was heated under 120oC for 24 h and then cooled to room temperature. Theresulting solution was directly purified by columnchromatography with petroleum ether/ethyl acetate (10:1) as eluent to give 1,3-diphenylpropan-1-one (5a) as awhite solid.
80%	With Cs₂CO₃ In toluene at 110℃; for 12h;
79%	With potassium hydroxide; 1-dodecene In 1,4-dioxane at 80℃; for 20h;
76%	With [Mn(HN(C₂H₄PⁱPr₂)₂)(CO)₂Br]; Cs₂CO₃ In tert-Amyl alcohol at 140℃; for 22h; Inert atmosphere;
76%	With potassium fluoride; tetrabutylammonium bromide; silver(I) bis(trifluoromethanesulfonyl)imide In water monomer at 90℃; for 16h; Inert atmosphere; Schlenk technique; Green chemistry;
76%	With sodium tertiary butoxide In toluene at 120℃; for 8h;
71%	With C₃₁H₃₆ClIrN₅⁽¹⁺⁾*C₂₄H₂₀B^(1-); potassium-t-butoxide In toluene at 100℃; for 6h;
70%	With bis[dichlorido(η⁵-1,2,3,4,5-pentamethyl-cyclopentadienyl)iridium(III)]; N-hexadecyl-N,N,N-trimethylammonium bromide; potassium hydroxide In tetrahydrofuran; water monomer at 40℃; for 20h; Inert atmosphere; Schlenk technique;
70%	With 2CF₃O₃S^(1-)*C₄₀H₃₀N₁₀Ni⁽²⁺⁾; lithium tert-butylate In toluene at 140℃; for 12h; Inert atmosphere; Schlenk technique;
67%	With tripotassium phosphate tribasic In neat (no solvent) at 175℃; for 24h; Sealed tube;
	With tripotassium phosphate tribasic In toluene at 125℃; for 21h; Inert atmosphere; Sonication;
	Stage #1: benzylic alcohol With 1,10-Phenanthroline; potassium-t-butoxide; nickel(II) bromide Inert atmosphere; Schlenk technique; Stage #2: 3-Methylacetophenone In toluene at 140℃; for 36h; Inert atmosphere; Schlenk technique;

Reference： [1]Liang, Yu-Feng; Zhou, Xin-Feng; Tang, Shi-Ya; Huang, Yao-Bing; Feng, Yi-Si; Xu, Hua-Jian [RSC Advances, 2013, vol. 3, # 21, p. 7739 - 7742]
[2]Wang, Rongzhou; Ma, Juan; Li, Feng [Journal of Organic Chemistry, 2015, vol. 80, # 21, p. 10769 - 10776]
[3]Liu, Pengcheng; Liang, Ran; Lu, Lei; Yu, Zhentao; Li, Feng [Journal of Organic Chemistry, 2017, vol. 82, # 4, p. 1943 - 1950]
[4]Bera, Jitendra K.; Laskar, Roshayed Ali; Nath, Anubhav; Patra, Kamaless [Organometallics, 2022]
[5]Wang, Dawei; Zhao, Keyan; Ma, Piming; Xu, Chongying; Ding, Yuqiang [Tetrahedron Letters, 2014, vol. 55, # 52, p. 7233 - 7235]
[6]Hu, Xinyu; Zhu, Haiyan; Sang, Xinxin; Wang, Dawei [Advanced Synthesis and Catalysis, 2018, vol. 360, # 22, p. 4293 - 4300]
[7]Cho, Chan Sik; Kim, Bok Tae; Kim, Tae-Jeong; Chul Shim, Sang [Tetrahedron Letters, 2002, vol. 43, # 44, p. 7987 - 7989]
[8]Peña-López, Miguel; Piehl, Patrick; Elangovan, Saravanakumar; Neumann, Helfried; Beller, Matthias [Angewandte Chemie - International Edition, 2016, vol. 55, # 48, p. 14967 - 14971][Angew. Chem., 2016, vol. 128, # 48, p. 15191 - 15195,5]
[9]Tao, Rong; Yang, Yike; Zhu, Haiyan; Hu, Xinyu; Wang, Dawei [Green Chemistry, 2020, vol. 22, # 23, p. 8452 - 8461]
[10]Luo, Lan; Liu, Hongqiang; Zeng, Wei; Hu, Wenkang; Wang, Dawei [Applied Organometallic Chemistry, 2022, vol. 36, # 2]
[11]Wang, Danfeng; McBurney, Roy T.; Pernik, Indrek; Messerle, Barbara A. [Dalton Transactions, 2019, vol. 48, # 37, p. 13989 - 13999]
[12]Rakers, Lena; Schäfers, Felix; Glorius, Frank [Chemistry - A European Journal, 2018, vol. 24, # 58, p. 15529 - 15532]
[13]Wu, Di; Wang, Yubin; Li, Min; Shi, Lei; Liu, Jichang; Liu, Ning [Applied Organometallic Chemistry, 2022, vol. 36, # 2]
[14]Charvieux, Aubin; Giorgi, Javier B.; Duguet, Nicolas; Métay, Estelle [Green Chemistry, 2018, vol. 20, # 18, p. 4210 - 4216]
[15]Chen, Benjamin Wei Jie; Chng, Leng Leng; Yang, Jun; Wei, Yifeng; Yang, Jinhua; Ying, Jackie Y. [ChemCatChem, 2013, vol. 5, # 1, p. 277 - 283]
[16]Cao, Yuanjie; Chen, Tieqiao; Huang, Tianzeng; Liu, Long [New Journal of Chemistry, 2020, vol. 44, # 21, p. 8697 - 8701]

25
[ 557-20-0 ]
[ 585-74-0 ]
[ 470665-32-8 ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: diethylzinc; 3-Methylacetophenone With titanium(IV) isopropylate; C₃₆H₄₈N₂O₆S₂ In toluene at 25℃; for 24h; Inert atmosphere; Stage #2: With water In toluene optical yield given as %ee; enantioselective reaction;	5.4. General procedure for ethylation of ketones General procedure: The bis(sulfonamide) diol 7 or 8 (5 mol %, 33 mg) was weighed into the reaction vessel and diethylzinc (1.0 M toluene, 1.6 equiv, 1.6 mL) and titanium(IV) isopropoxide (1.2 equiv, 1.2 mL) were added at room temperature. After 10 min, the substrate ketone (1.0 equiv, 1 mmol) was added neat or as a solution in toluene (1 mL). The homogeneous reaction mixture was stirred at room temperature. After 24 h the reaction was quenched with H2O (5 mL), diluted with EtOAc, filtered through Celite, and layers separated. The aqueous layer was extracted with EtOAc (2×40 mL) and the combined organic layers were washed with brine, dried over MgSO4, and concentrated in under reduced pressure. The resulting residue was purified by flash chromatography on deactivated silica gel (Et3N/SiO2=2.5% v/v, hexanes/EtOAC 95:5) to afford the ethyl addition products. These alcohols were fully characterized and compared with the data reported in the literature. The ee value was determined by HPLC on a Daicel OD-H or AD-H column.
	With titanium(IV) isopropylate; (R,R)-C₆H₄-bis((1S)-camphosulfonylamide) In hexane at 20℃;

Reference： [1]Location in patent: experimental part Huelgas, Gabriela; Larochelle, Lynne K.; Rivas, Lucrecia; Luchinina, Yekaterina; Toscano, Rubén A.; Carroll, Patrick J.; Walsh, Patrick J.; Anaya De Parrodi, Cecilia [Tetrahedron, 2011, vol. 67, # 24, p. 4467 - 4474]
[2]Mukaiyama, Teruaki; Shintou, Taichi; Fukumoto, Kentaro [Journal of the American Chemical Society, 2003, vol. 125, # 35, p. 10538 - 10539]

26
[ 585-74-0 ]
[ 620-14-4 ]
[ 7287-81-2 ]

Reference： [1]Chemical Communications,2003,p. 514 - 515

27
[ 100-80-1 ]
[ 620-23-5 ]
[ 585-74-0 ]

Yield	Reaction Conditions	Operation in experiment
83%	With tert.-butylhydroperoxide; air; (Pd(IiPr)Cl₂)2 In methanol at 35℃; for 32h;

Reference： [1]Cornell, Candace N.; Sigman, Matthew S. [Journal of the American Chemical Society, 2005, vol. 127, # 9, p. 2796 - 2797]

28
[ 557-20-0 ]
[ 585-74-0 ]
m-tolylbutan-2-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With titanium(IV) isopropylate; 1R,2R-[(1S,2R,4R-2-OH-7,7-Me₂-bicycloheptyl)CH₂SO₂NH]2C₆H₁₀ In hexane; toluene at 20℃; for 12h;
79%	With titanium(IV) isopropylate; (R,R)-bissulfonamide diol ligand at 20℃; for 4h;
78%	Stage #1: diethylzinc; 3-Methylacetophenone With titanium(IV) isopropylate; (1S,2R,4R,1'R,2'R,1''S,2''R,4''R)-N-{trans-2'-[2''-hydroxy-7'',7''-dimethylbicyclo[2.2.1]hept-1''-ylmethylsulfonamino]cyclohexyl}-2-hydroxy-7,7-dimethylbicyclo[2.2.1]hept-1-ylmethanesulfonamide In toluene at 20℃; for 18h; Inert atmosphere; Stage #2: With ammonium chloride In water; toluene optical yield given as %ee; enantioselective reaction;	5.4.1. Probing non-linear behavior General procedure: The reactions were performed using 10 mol % of ligand 1 to facilitate accurate weighing of the enantiomeric ligands. The enantiomeric ligands were individually weighted and combined in the reaction vessel. The diethylzinc solution (1.0 M in toluene, 1.6 equiv) and the titanium(IV) isopropoxide (1.4 M toluene solution, 1.2 equiv) were added at room temperature. After 5-10 min, the acetophenone (1.0 equiv) was added neat. The homogeneous reaction mixture was stirred at room temperature for 18 h. After completion, the reaction mixture was quenched with saturated aqueous solution NH4Cl, extracted into CH2Cl2, concentrated under reduced pressure, and purified by column chromatography. The ee was determined by GC using Supelco β-Dex 120 column and nitrogen carrier gas (t1=25.8 min, t2=26.7 min, 110 °C, 1.0 mL/min).

Reference： [1]Jeon, Sang-Jin; Li, Hongmei; Garcia, Celina; LaRochelle, Lynne K.; Walsh, Patrick J. [Journal of Organic Chemistry, 2005, vol. 70, # 2, p. 448 - 455]
[2]Jeon, Sang-Jin; Li, Hongmei; Walsh, Patrick J. [Journal of the American Chemical Society, 2005, vol. 127, # 47, p. 16416 - 16425]
[3]Location in patent: experimental part Huelgas, Gabriela; Larochelle, Lynne K.; Rivas, Lucrecia; Luchinina, Yekaterina; Toscano, Rubén A.; Carroll, Patrick J.; Walsh, Patrick J.; Anaya De Parrodi, Cecilia [Tetrahedron, 2011, vol. 67, # 24, p. 4467 - 4474]

29
[ 620-14-4 ]
(S)-1-(3-methylphenyl)ethanol [ No CAS ]
(R)-(+)-1-(3-methylphenyl)-1-ethanol [ No CAS ]
[ 585-74-0 ]

Yield	Reaction Conditions	Operation in experiment
	With 1H-imidazole; [bis(acetoxy)iodo]benzene; C84H72ClFeN4O12S4(4-)*4Na(1+); In methanol; water; for 1h;Inert atmosphere;	General procedure: Iron porphyrin complex 1 (1.6 mg, 1 mumol) and imidazole (0.68 mg, 10 mumol) was placed in a test tube under argon. Then, 0.8 ml of distilled methanol and 0.2 ml H2O were added, followed by ethylbenzene (106 mg, 1 mmol). PhI(OAc)2, (32 mg, 100 mumol) in 0.2 ml methanol was added over a period of 45 mn. After 1 h, the mixture was analysed by GC for oxidation yield, 46%, based on oxidant, and for epoxide enantiomeric excess, 75%. Polarimetric measurement of the oxidation product determined that (S)-(-)-1-phenylethanol was formed in excess. In addition to expected phenylethanol, acetophenone was also observed.The reaction and analysis of the other susbtrates in Table 1 were carried out in a manner identical with that used for ethylbenzene oxidation except for indane and tetrahydronaphtalene. In the latter case, enantiomeric excess was determined by chiral HPLC with a Chiralcel OB-H column: n-hexane/isopropanol=95/5; flow rate=0.5 ml min-1; wavelength=220 nm.
	With 1H-imidazole; chloro(5,10,15,20-tetrakis(10-nitro-1,2,3,4,5,6,7,8-octahydro-1,4;5,8-dimethanoanthracen-9-yl)porphyrin) manganese(III); dihydrogen peroxide; In methanol; dichloromethane; for 2h;Inert atmosphere;	Manganese porphyrin complex 9 (1.4 mg, 1 mumol) and imidazole (0.14 mg, 4 mumol) were placed in a test tube under argon. Then, 1 ml of distilled CH2Cl2 was added, followed by <strong>[620-14-4]3-ethyltoluene</strong> (4.80 mg, 40 mumol). H2O2 (19.4 mg, 200 mumol) and imidazole (0.68 mg, 20 mumol) in 0.1 ml MeOH were added over a period of 1 h with a syringe-pump. After the addition of all the H2O2, the reaction mixture was allowed to stir for an additional 1 h. The mixture was analyzed by GC for oxidation yield, 33 %, alcohol/ketone ratio, 52:48, and alcohol enantiomeric excess, 21 % (conditions used: 80 C ( 1min), 1 C min-1 80-120 C, 2.5 C min-1 120-180 C). The reaction and analysis of the other substrates and catalysts in Table 4 was carried out in an identical manner with that used for <strong>[620-14-4]3-ethyltoluene</strong> oxidation. Except for indane, the enantiomeric excess was determined by chiral HPLC with a Chiralcel OB-H column: n-hexane/isopropanol 95:5; flow rate: 0.5 ml min-1, detection: 220 nm.

Reference： [1]Tetrahedron Asymmetry,2005,vol. 16,p. 3520 - 3526
[2]Tetrahedron,2012,vol. 68,p. 5824 - 5828
[3]Tetrahedron,2014,vol. 70,p. 8836 - 8842

30
[ 620-14-4 ]
[ 585-74-0 ]

Yield	Reaction Conditions	Operation in experiment
	With tert.-butylhydroperoxide; In N,N-dimethyl-formamide; at 80℃; for 20h;Schlenk technique;	General procedure: The oxidation of alkanes (e.g., ethylbenzene) was conducted in a 25-mL Schlenk tube. Typically, ethylbenzene (0.5 mmol), catalyst (10 mol% based on Ni), tert-butyl hydroperoxide (TBHP; 1.5 mmol), and DMF (2 mL) were added to the tube and heated at 80 C. After reaction, the catalyst was isolated from the mixture solution by centrifugation, then washed with DMF and methanol. The liquid mixtures were then analyzed by gas chromatography mass spectrometry (Agilent Technologies 7890B-5977A) on a chromatograph equipped with a 0.25 mm × 30 m HP-5MS capillary column.

Reference： [1]Chemical Communications,2018,vol. 54,p. 3701 - 3704
[2]Applied Organometallic Chemistry,2017,vol. 31
[3]Journal of Organic Chemistry,2020,vol. 85,p. 4324 - 4334
[4]Organic Letters,2005,vol. 7,p. 4549 - 4552
[5]Cuihua Xuebao/Chinese Journal of Catalysis,2016,vol. 37,p. 955 - 962
[6]Angewandte Chemie - International Edition,2019,vol. 58,p. 16490 - 16494
Angew. Chem.,2019,vol. 131,p. 16642 - 16646,5

31
[ 14633-54-6 ]
[ 585-74-0 ]
1-(3-methylphenyl)-1-[1-phenylthiocyclopropyl]ethanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	Stage #1: cyclopropylphenylsulfide With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 5h; Stage #2: 3-Methylacetophenone In tetrahydrofuran; hexane at -78℃; for 14h;

Reference： [1]Bernard, Angela M.; Frongia, Angelo; Secci, Francesco; Piras, Pier P. [Chemical Communications, 2005, # 30, p. 3853 - 3855]

32
[ 7287-81-2 ]
rel-(R)-1-(m-methylphenyl)ethanol [ No CAS ]
[ 585-74-0 ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5565 - 5567
[2]Green Chemistry,2012,vol. 14,p. 1289 - 1292
[3]Angewandte Chemie - International Edition,2018,vol. 57,p. 2085 - 2090
Angew. Chem.,2018,vol. 130,p. 2107 - 2112,6

33
[ 7287-81-2 ]
(S)-1-(3-methylphenyl)ethanol [ No CAS ]
(R)-(+)-1-(3-methylphenyl)-1-ethanol [ No CAS ]
[ 585-74-0 ]

Reference： [1]Organic Letters,2007,vol. 9,p. 865 - 868
[2]Angewandte Chemie - International Edition,2018,vol. 57,p. 2085 - 2090
Angew. Chem.,2018,vol. 130,p. 2107 - 2112,6

34
[ 67-63-0 ]
[ 585-74-0 ]
[ 7287-81-2 ]
[ 67-64-1 ]

Reference： [1]Journal of Organometallic Chemistry,2007,vol. 692,p. 2306 - 2313
[2]Journal of Organometallic Chemistry,2009,vol. 694,p. 3068 - 3075
[3]Chemistry - A European Journal,2011,vol. 17,p. 4737 - 4741

35
[ 585-74-0 ]
[ 23040-54-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With hydroxylamine hydrochloride; sodium acetate In ethanol; water at 95℃;
93.6%	With hydroxylamine hydrochloride; sodium carbonate In ethanol; water at 25℃; for 2h;	3 Example 3: Preparation of 3-methylacetophenone oxime Add 3-methylacetophenone (10.0g, 74.5mmol) to a 250mL reaction flask.hydroxylamine hydrochloride (7.8g, 112mmol), 80mL ethanol, then, a 20% sodium carbonate aqueous solution (59.0 g, 112 mmol) was added dropwise, and the mixture was reacted at 25 °C for 4 hours. after the reaction, the solvent was distilled off under reduced pressure, washed with water, filtered with suction, and dried to obtain 10.4 g of 3-methylacetophenone oxime as a white solid with a yield of 93.6%.
76%	With pyridine; hydroxylamine hydrochloride at 80℃; for 0.25h;

68%	With hydroxylamine hydrochloride; sodium hydroxide In methanol at 20℃; Green chemistry;
	With sodium hydroxide; hydroxylamine hydrochloride In ethanol for 1h; Heating;
	With hydroxylamine hydrochloride; triethylamine In ethanol at 120℃; for 0.333333h; Microwave irradiation;
	With hydroxylamine hydrochloride; sodium acetate In ethanol; water Reflux;
	With pyridine; hydroxylamine hydrochloride at 20℃; for 8h;
	With hydroxylamine hydrochloride
	With hydroxylamine hydrochloride; sodium acetate In methanol at 60℃; for 2h;
	With hydroxylamine hydrochloride; sodium acetate In ethanol; water for 16h; Reflux; Inert atmosphere;
	With hydroxylamine hydrochloride; sodium acetate In ethanol; water at 100℃;
	With hydroxylamine hydrochloride; sodium acetate In methanol at 20℃; Inert atmosphere; Schlenk technique;
	With hydroxylamine hydrochloride; sodium acetate In ethanol; water at 100℃;
	With hydroxylamine hydrochloride; sodium acetate In ethanol; water at 100℃;
	With hydroxylamine hydrochloride; sodium acetate In ethanol; water at 100℃; for 6h;
	With hydroxylamine hydrochloride; sodium acetate In ethanol; water Reflux;
	With hydroxylamine hydrochloride; sodium acetate In methanol; water at 120℃; for 2h;
	With hydroxylamine hydrochloride; sodium acetate In methanol at 60℃; for 2h;
	With hydroxylamine hydrochloride; sodium acetate In methanol at 80℃; for 3h; Inert atmosphere;
	Stage #1: 3-Methylacetophenone With hydroxylamine hydrochloride In ethanol; water at 20℃; for 0.25h; Stage #2: With sodium hydroxide In ethanol; water at 0 - 20℃; for 1.5h;
	With hydroxylamine hydrochloride; sodium acetate In ethanol at 95℃; Inert atmosphere; Glovebox;
	With hydroxylamine hydrochloride; sodium acetate In ethanol at 80℃;

Reference： [1]Wang, Qiang; Wang, Fen; Yang, Xifa; Zhou, Xukai; Li, Xingwei [Organic Letters, 2016, vol. 18, # 23, p. 6144 - 6147]
[2]Current Patent Assignee: CHANGZHOU UNIVERSITY - CN110317177, 2019, A Location in patent: Paragraph 0063; 0064
[3]Neufeldt, Sharon R.; Sanford, Melanie S. [Organic Letters, 2010, vol. 12, # 3, p. 532 - 535]
[4]Aakeroey, Christer B.; Sinha, Abhijeet S. [RSC Advances, 2013, vol. 3, # 22, p. 8168 - 8171]
[5]Park, Adriana; Kosareff, Nicole M.; Kim, Jason S.; De Lijser, H. J. Peter [Photochemistry and Photobiology, 2006, vol. 82, # 1, p. 110 - 118]
[6]Location in patent: experimental part Lovering, Frank; Kirincich, Steve; Wang, Weiheng; Combs, Kerry; Resnick, Lynn; Sabalski, Joan E.; Butera, John; Liu, Julie; Parris, Kevin; Telliez [Bioorganic and Medicinal Chemistry, 2009, vol. 17, # 9, p. 3342 - 3351]
[7]Shen, Ke; Liu, Xiaohua; Cai, Yunfei; Lin, Lili; Feng, Xiaoming [Chemistry - A European Journal, 2009, vol. 15, # 24, p. 6008 - 6014]
[8]Zhang, Xingping; Chen, Dan; Zhao, Miao; Zhao, Jing; Jia, Aiqun; Li, Xingwei [Advanced Synthesis and Catalysis, 2011, vol. 353, # 5, p. 719 - 723]
[9]Wang, Qiu-Shi; Xie, Jian-Hua; Li, Wei; Zhu, Shou-Fei; Wang, Li-Xin; Zhou, Qi-Lin [Organic Letters, 2011, vol. 13, # 13, p. 3388 - 3391]
[10]Feng, Chao; Feng, Daming; Loh, Teck-Peng [Chemical Communications, 2014, vol. 50, # 69, p. 9865 - 9868]
[11]Sen, Malay; Kalsi, Deepti; Sundararaju, Basker [Chemistry - A European Journal, 2015, vol. 21, # 44, p. 15529 - 15533]
[12]Zhu, Zhongzhi; Tang, Xiaodong; Li, Xianwei; Wu, Wanqing; Deng, Guohua; Jiang, Huanfeng [Journal of Organic Chemistry, 2016, vol. 81, # 4, p. 1401 - 1409]
[13]Muralirajan, Krishnamoorthy; Kuppusamy, Ramajayam; Prakash, Sekar; Cheng, Chien-Hong [Advanced Synthesis and Catalysis, 2016, vol. 358, # 5, p. 774 - 783]
[14]Zhu, Zhongzhi; Tang, Xiaodong; Li, Jianxiao; Li, Xianwei; Wu, Wanqing; Deng, Guohua; Jiang, Huanfeng [Chemical Communications, 2017, vol. 53, # 22, p. 3228 - 3231] Zhu, Zhongzhi; Tang, Xiaodong; Cen, Jinghe; Li, Jianxiao; Wu, Wanqing; Jiang, Huanfeng [Chemical Communications, 2018, vol. 54, # 30, p. 3767 - 3770]
[15]Zhu, Zhongzhi; Tang, Xiaodong; Li, Jianxiao; Li, Xianwei; Wu, Wanqing; Deng, Guohua; Jiang, Huanfeng [Organic Letters, 2017, vol. 19, # 6, p. 1370 - 1373]
[16]Luo, Beibei; Weng, Zhiqiang [Chemical Communications, 2018, vol. 54, # 76, p. 10750 - 10753]
[17]Chen, Yuesu; Cantillo, David; Kappe, C. Oliver [European Journal of Organic Chemistry, 2019, vol. 2019, # 11, p. 2163 - 2171]
[18]Xiao, Fuhong; Yuan, Shanshan; Huang, Huawen; Zhang, Feng; Deng, Guo-Jun [Organic Letters, 2019, vol. 21, # 21, p. 8533 - 8536]
[19]Cao, Hao-Qiang; Liu, Hao-Nan; Liu, Zhe-Yuan; Ma, Jun-An; Qiao, Bao-Kun; Zhang, Fa-Guang [Chemistry - A European Journal, 2020, vol. 26, # 24, p. 5515 - 5521]
[20]Meng, Huanxin; Xu, Zhenhua; Qu, Zhonghua; Huang, Huawen; Deng, Guo-Jun [Organic Letters, 2020, vol. 22, # 15, p. 6117 - 6121]
[21]Li, Yuan; Fang, Feifei; Zhou, Jianhui; Li, Jiyuan; Wang, Run; Liu, Hong; Zhou, Yu [Advanced Synthesis and Catalysis, 2021, vol. 363, # 13, p. 3305 - 3310]
[22]Chang, Junbiao; Deng, Wei-Qiao; Kong, Lingheng; Li, Xingwei; Liu, Bingxian; Sun, Lincong; Wang, Fen; Zhao, Yanlian [Chemical Communications, 2021, vol. 57, # 67, p. 8268 - 8271]
[23]Liang, Jingwen; Rao, Yingqi; Zhu, Weidong; Wen, Tingting; Huang, Junjie; Chen, Zhichao; Chen, Lu; Li, Yibiao; Chen, Xiuwen; Zhu, Zhongzhi [Organic Letters, 2021, vol. 23, # 18, p. 7028 - 7032]

36
potassium cyanide [ No CAS ]
[ 1066-33-7 ]
[ 585-74-0 ]
[ 652992-46-6 ]

Yield	Reaction Conditions	Operation in experiment
	With ammonia; In ethanol; water; at 60℃;	To a solution of 930 mg 3'-methylacetophenone in 5 mL anhydrous ethanol was added 2.04 g [NH4HC03,] 542 mg KCN, then 2.1 mL conc. NH40H. The mixture was stirred at [60C] overnight. Addition of water and partial solvent removal induced crystallization. The product was vacuum filtered and washed several times with water. The resultant white solid was recrystallized from [MEOH] to yield 5- [METHYL-5- (3-METHYLPHENYL)-IMIDAZOLIDINE-2,] 4-dione as a white solid.

Reference： [1]Patent: WO2004/11448,2004,A1 .Location in patent: Page 69

Yield	Reaction Conditions	Operation in experiment
7%		Example E28 A mixture of 10 millimoles of 3-ethyltoluene, 1-millimole of N-hydroxyphthalimide, 0.05 millimole of copper acetate (Cu(OAc)2) and 25 milliliters of acetonitrile was stirred, in an oxygen atmosphere, at 75 C. for six hours. As a result, 3-ethyltoluene was transformed into m-methylacetophenone (yield 57%) and 3-ethylbenzoic acid (yield 7%) with a transformation rate of 90 percent.
6%		Example E29 To 25 milliliters of acetic acid were added 10 millimoles of 3-ethyltoluene, 1 millimole of N-hydroxyphthalimide and 0.05 millimole of acetylacetonatocobalt(II) Co(AA)2. The resultant mixture was stirred, in an oxygen atmosphere, at 75 C. for six hours. With a transformation rate of 93 percent, 3-ethyltoluene was transformed into m-methylacetophenone (yield 55%) and 3-ethylbenzoic acid (yield 6%).

38
[ 100-80-1 ]
[ 585-74-0 ]

Yield	Reaction Conditions	Operation in experiment
99%	With tert.-butylhydroperoxide; C₂₁H₁₉N₅Pd⁽²⁺⁾*2BF₄^(1-) In decane; acetonitrile at 45℃; for 12h;
91%	With dihydrogen peroxide In water; acetonitrile at 55℃; for 12h;	2.4. General procedure for Wacker oxidation of olefins General procedure: With the dissolution of substrate (0.4 mmol) in CH 3 CN (2 mL), Pd0/RGO (0.01 g), H 2 O (0.5 mL), and GO (0.01 g) were orderly added into apressure bottle (35 mL). The mixture was dispersed by ultrasound forabout 30 min at 25 °C. Then H 2 O 2 (30 wt%, 4 mmol) was cautiously added dropwise. Immediately, the reaction system was heated to 55 °Cwith lid closed until the process was fully completed (detected by TLC).Subsequently, Pd0/RGO and GO were removed by centrifuge. Themixture was extracted by deionized water and ethyl acetate. After thelayers were separated, the organic part was washed with deionizedwater, dried with anhydrous NaSO 4 , ltered and evaporated by reducedpressure distillation. Finally, purication of the crude product wascarried out by column chromatography. For 14, 18, 24, 40 (Table 2),excess hydrogen peroxide was added after half of the total reaction time.
89%	With dihydrogen peroxide; C₂₁H₂₄Cl₂N₄O₉Pd In water at 80℃; regioselective reaction;	4.4 General Procedure for the Wacker OxidationReaction in the Presence of the GPT-Pdor GPT-Pt Catalyst General procedure: The Wacker oxidation reaction was performed in a 10 mLround-bottomed flask where olefins (1.0 mmol), H2O2(2.0 mmol), GPT-Pd or GPT-Pt catalyst (1 mol% withrespect to olefins) and water (2 mL) were charged and stirredat 80 °C under air. The reaction progress was monitoredby TLC. After completion of the reaction, the mixture wasallowed to cool to room temperature. Then the aqueousphase was extracted with CH2Cl23 times (3 × 2 mL). Thenthe combined organic layers were dried over anhydrousNa2SO4,concentrated under vacuum and purified by columnchromatography (n-hexane/ethyl acetate, 10:1) to afford thedesired product.

83%	With oxygen; sodium acetate; palladium dichloride In [1,3]-dioxolan-2-one; water at 100℃; for 24h; Autoclave;
82%	With perchloric acid; oxygen; palladium diacetate; p-benzoquinone; sodium nitrite In methanol; water at 20℃; for 5h; Schlenk technique; Sealed tube; Green chemistry;
69%	With manganese(II) bromide; water; lithium perchlorate; copper dichloride In acetonitrile at 60℃; for 8h; Sealed tube; Inert atmosphere; Electrochemical reaction; regioselective reaction;
93%Chromat.	With oxygen; copper(l) chloride In ethanol; water; 1,3,5-trimethyl-benzene at 75℃; for 36h;
	With oxygen; copper(l) chloride; palladium dichloride In methanol; water at 20℃; for 16h;
90 %Chromat.	With (2-(2-pyridyl)benzoxazole)Pd(MeCN)2(OTf)2; dihydrogen peroxide In water; acetonitrile at 27℃; for 24h;
65 %Chromat.	With [(2-(pyridin-2-yl)naphtho[1,2-d]oxazole)Pd(NCMe)₂][OTf]₂; water; oxygen In methanol at 27℃; for 24h; Inert atmosphere;
	Multi-step reaction with 2 steps 1: lithium aluminium tetrahydride; iron(III) chloride; hydrogen / tetrahydrofuran / 24 h / 23 °C 2: NADPH; 9‑mesityl-10-methylacridinium perchlorate; oxygen; ketoreductase-P1-B12 / acetonitrile; water / 24 h / 23 °C / Irradiation; Enzymatic reaction
84.3 %Chromat.	With oxygen; potassium carbonate; isopropyl alcohol at 150℃; for 6h; regioselective reaction;

Reference： [1]Bera, Jitendra K.; Dutta, Indranil; Kunnikuruvan, Sooraj; Reshi, Noor U Din; Saha, Sayantani; Yadav, Suman [ACS Catalysis, 2020, vol. 10, # 19, p. 11385 - 11393]
[2]Gao, Xi; Zhou, Jianhao; Peng, Xinhua [Catalysis Communications, 2019, vol. 122, p. 73 - 78]
[3]Shen, Chao; Sun, Nabo; Wu, Huizhen; Xu, Hao; Yu, Wenbo; Zheng, Kai [Catalysis Letters, 2022]
[4]Location in patent: experimental part Wang, Jing-Lun; He, Liang-Nian; Miao, Cheng-Xia; Li, Yu-Nong [Green Chemistry, 2009, vol. 11, # 9, p. 1317 - 1320]
[5]Zhang, Guofu; Xie, Xiaoqiang; Wang, Yong; Wen, Xin; Zhao, Yun; Ding, Chengrong [Organic and Biomolecular Chemistry, 2013, vol. 11, # 18, p. 2947 - 2950]
[6]Lai, Junshan; Pericàs, Miquel A. [Organic Letters, 2020, vol. 22, # 18, p. 7338 - 7342]
[7]Byun, Sangmoon; Chung, Jooyoung; Jang, Youngjin; Kwon, Jungmin; Hyeon, Taeghwan; Kim, B. Moon [RSC Advances, 2013, vol. 3, # 37, p. 16296 - 16299]
[8]Sato, Hirofumi; Hummel, Werner; Gröger, Harald [Angewandte Chemie - International Edition, 2015, vol. 54, # 15, p. 4488 - 4492][Angew. Chem., 2015, vol. 127, # 15, p. 4570 - 4574]
[9]Cao, Qun; Bailie, David S.; Fu, Runzhong; Muldoon, Mark J. [Green Chemistry, 2015, vol. 17, # 5, p. 2750 - 2757]
[10]Chai, Hongxin; Cao, Qun; Dornan, Laura M.; Hughes, N. Louise; Brown, Clare L.; Nockemann, Peter; Li, Jiarong; Muldoon, Mark J. [European Journal of Inorganic Chemistry, 2017, vol. 2017, # 47, p. 5604 - 5608]
[11]Betori, Rick C.; May, Catherine M.; Scheidt, Karl A. [Angewandte Chemie - International Edition, 2019, vol. 58, # 46, p. 16490 - 16494][Angew. Chem., 2019, vol. 131, p. 16642 - 16646,5]
[12]An, Yue; Chen, Bo; Gao, Shuang; Huang, Guanwang; Luo, Huihui; Shang, Sensen; Wang, Lianyue [Catalysis science and technology, 2020, vol. 10, # 9, p. 2769 - 2773]

39
[ 95-92-1 ]
[ 585-74-0 ]
[ 741286-41-9 ]

Yield	Reaction Conditions	Operation in experiment
82%	Stage #1: oxalic acid diethyl ester With sodium methylate In diethyl ether at 20℃; Inert atmosphere; Stage #2: 3-Methylacetophenone In diethyl ether at 20℃; for 12h;
70%	Stage #1: 3-Methylacetophenone With lithium hexamethyldisilazane In tetrahydrofuran at -20 - 0℃; for 1h; Inert atmosphere; Stage #2: oxalic acid diethyl ester In tetrahydrofuran at -20 - 20℃; for 2h;	To a solution of 1-(m-tolyl)ethan-1-one (5.0 g, 37.3 mmol) in THF (80 mL) was cooled to -20oC under N2atmosphere. Then, LHMDS (1M, 56 mL, 56.0 mmol) was added slowly to maintain the internal temperature at -20oC. Afterward, the reaction was warmed to 0oC and stirred for 1 hour.The reaction was cooled down to -20oC again, and into which diethyl oxalate (6.0 g, 41.1 mmol) was added slowly. The resulting mixture was allowed to warm to room temperature and stirred for another 2 hours and then diluted with ethyl acetate (20 mL), followed by addition of HCl (1 M) solution to adjust pH = 5~6. The mixture was washed by water (30 mL x3) and brine (30 mL x3), dried over Na2SO4, filtered and concentrated under reduced pressure. The residue waspurified by chromatography on silica gel eluting with petroleum ether: ethyl acetate = 5:1-3:1 to get the desired product (6.1 g, 70.0%) as a slight yellow solid.
	With sodium methylate In diethyl ether at 20℃; for 15h;

	With sodium ethanolate In ethanol at 0 - 20℃;
	With sodium ethanolate In ethanol at 120℃; for 0.333333h; Sealed tube; Microwave irradiation;
	With sodium ethanolate In ethanol at 0 - 20℃;
	With sodium hydride In toluene at 90℃; for 2h;	5.2.8 General procedure for the synthesis of intermediates 14 General procedure: A round-bottom flask equipped with a magnetic stirrer was charged with alkanone 13 (3.5mmol), diethyl oxalate (0.73g, 5mmol) and toluene (15mL), and a suspension of NaH (80%, 0.21g, 7mmol) was added. The reaction mixture was stirred at 90°C for 2h. The reaction mixture was poured into ice-water (30mL), acidified with aqueous HCl to pH 2-3 and extracted with EtOAc. The combined organic layer was dried over Na2SO4 and evaporated under reduced pressure. The resulting residue was then purified by flash column chromatography on silica using 10% ethyl acetate in petroleum ether. Yield 75-85%
	With ethanol; sodium at 0 - 20℃; for 4h;	4.1.5 (Z)-3-(2-(Naphthalen-1-yl)-2-oxoethylidene)-3,4-dihydroquinoxalin-2(1H)-one (J46) General procedure: Compound J46 was prepared as previously reported [37]. Briefly, sodium (17.4mmol, 400mg) was added to a solution of ethanol (100mL) in portions and the mixture was stirred for 1h. The newly prepared sodium ethanol/ethanol solution was obtained. A mixture solvent of α-naphthalene ethyl ketone (10mmol, 1.70g) and oxalic acid diethyl ester (15mmol, 2.19g) was dropwise added to the aforesaid sodium ethanol/ethanol solution at 0°C and stirred for another 4hat room temperature. Then, the mixture was poured into ice water and the pH value was adjusted to 2.0 with hydrochloric acid (2M). The obtained solid was filtered and washed with water (10mL), and the crude product ethyl 4-(naphthalen-1-yl)-2,4-dioxobutanoate was used for the next step without purification. A solution of the former crude product (2.0mmol, 540mg) and o-phenylenediamine (2mmol, 216mg) in ethanol (10mL) was stirred for 4hat room temperature. The yellow solid was filtered, and the filter cake was washed with ethanol (10mL) and water (10mL) in sequence and then recrystallized from a mixture solvent of DMF/ethanol (15:1) to give J46 as a yellow solid. Yield: 26%.
	With sodium ethanolate In ethanol at 0 - 20℃;
	With sodium ethanolate In ethanol at 0 - 20℃; for 15h;
	With sodium ethanolate In ethanol at 0 - 20℃; Inert atmosphere; Schlenk technique;
	With sodium ethanolate In ethanol at 20 - 80℃; for 24.5h;	4.1. General procedure for the synthesis of 2,4-dioxo-4-phenylbutanoate derivatives 3 General procedure: A mixture of acetophenone derivatives 1 (10 mmol) and diethyl oxalate 2 (10 mmol) was added to freshly prepared solu- tion EtONa/EtOH (10 mmol Na in 10 mL ethanol) in a dropwise manner at room temperature and obtained mixture was stirred at room temperature for 24 h. Then, the mixture was heated at 80 °for 30 min. After that, pH of the latter mixture was set at pH = 2 using sulphuric acid and the organic phase was extracted by dichloromethane and dried over Na 2 SO 4 and the solvent was evaporated under reduced pressure. The obtained residue was re- crystallized in ethanol to give pure 2,4-dioxo-4-phenylbutanoate derivatives 3 .

Reference： [1]Location in patent: experimental part Nagarapu, Lingaiah; Gaikwad, Hanmant K.; Sarikonda, Kartheeka; Mateti, Jhansi; Bantu, Rajashaker; Raghu; Manda, Krishna Madhuri; Kalvendi, Shasi Vardhan [European Journal of Medicinal Chemistry, 2010, vol. 45, # 11, p. 4720 - 4725]
[2]Current Patent Assignee: ACURASTEM - WO2021/163727, 2021, A1 Location in patent: Page/Page column 201
[3]Location in patent: scheme or table Nagarapu, Lingaiah; Mateti, Jhansi; Gaikwad, Hanmant K.; Bantu, Rajashaker; Sheeba Rani; Prameela Subhashini [Bioorganic and Medicinal Chemistry Letters, 2011, vol. 21, # 14, p. 4138 - 4140]
[4]Goli-Garmroodi, Fereshteh; Omidi, Marzieh; Saeedi, Mina; Sarrafzadeh, Farhad; Rafinejad, Ali; Mahdavi, Mohammad; Bardajee, Ghasem Rezanejade; Akbarzadeh, Tahmineh; Firoozpour, Loghman; Shafiee, Abbas; Foroumadi, Alireza [Tetrahedron Letters, 2015, vol. 56, # 5, p. 743 - 746]
[5]Waterson, Alex G.; Kennedy, J. Phillip; Patrone, James D.; Pelz, Nicholas F.; Feldkamp, Michael D.; Frank, Andreas O.; Vangamudi, Bhavatarini; Souza-Fagundes, Elaine M.; Rossanese, Olivia W.; Chazin, Walter J.; Fesik, Stephen W. [ACS Medicinal Chemistry Letters, 2015, vol. 6, # 2, p. 140 - 145]
[6]Ghaedi; Bardajee; Mirshokrayi; Mahdavi; Shafiee; Akbarzadeh [RSC Advances, 2015, vol. 5, # 109, p. 89652 - 89658]
[7]Bi, Fangchao; Song, Di; Zhang, Nan; Liu, Zhiyang; Gu, Xinjie; Hu, Chaoyu; Cai, Xiaokang; Venter, Henrietta; Ma, Shutao [European Journal of Medicinal Chemistry, 2018, vol. 159, p. 90 - 103]
[8]Dou, Xiaodong; Huang, Huixia; Jiang, Lan; Jiao, Ning; Jin, Hongwei; Liu, Zhenming; Zhang, Liangren; Zhang, Lihe; Zhu, Guiwang [European Journal of Medicinal Chemistry, 2020, vol. 201]
[9]Ghaedi, Aseyeh; Bardajee, Ghasem Rezanejade; Delbari, Akram Sadat; Hekmat, Shohreh [Arkivoc, 2020, vol. 2020, # 6]
[10]Saeedi, Mina; Eslami, Azadeh; Mirfazli, Seyedeh Sara; Zardkanlou, Mahsa; Faramarzi, Mohammad Ali; Mahdavi, Mohammad; Akbarzadeh, Tahmineh [Letters in drug design and discovery, 2021, vol. 18, # 5, p. 436 - 444]
[11]Hu, Zi-Qi; Li, Xiang; Liu, Li-Xia; Yu, Chang-Bin; Zhou, Yong-Gui [Journal of Organic Chemistry, 2021, vol. 86, # 23, p. 17453 - 17461]
[12]Adib, Mehdi; Azizian, Homa; Biglar, Mahmood; Faramarzi, Mohammad Ali; Gashghaee, Mojtaba; Larijani, Bagher; Mahdavi, Mohammad; Mohammadi-Khanaposhtani, Maryam; Mojtabavi, Somayeh; Rastegar, Hossein; Rezaei, Yahya [Journal of Molecular Structure, 2022, vol. 1257]

40
[ 585-74-0 ]
[ 586-42-5 ]

Reference： [1]Advanced Synthesis and Catalysis,2009,vol. 351,p. 1677 - 1684

41
[ 766-82-5 ]
[ 585-74-0 ]

Yield	Reaction Conditions	Operation in experiment
98%	With anhydrous silver tetrafluoroborate; lithium hydroxide monohydrate In glacial acetic acid at 110℃; for 10h; regioselective reaction;	3 4.2. General procedure for the synthesis of methyl ketones (2a-x). 4.2.3. 1-(m-Tolyl)ethanone (2c) General procedure: To the mixture of terminal alkyne (1mmol), water (2.0 equiv), and acetic acid (2 mL), silver tetrafluoroborate (5 mol%) was added. The mixture was stirred at 110°C for 10 h. Water (10 mL) was added and the solution was extracted with ethyl acetate (3×8 mL), the combined extract was dried with anhydrous MgSO4. The solvent was removed and the crude product was separated by column chromatography to give the pure sample. 4.2.3. 1-(m-Tolyl)ethanone (2c). 1H NMR (400 MHz, CDCl3): δ=7.75 (d, J=10.8 Hz, 2H), 7.33 (t, J=8.0 Hz, 2H), 2.58 (s, 3H), 2.40 (s, 3H). 13C NMR (100 MHz, CDCl3): δ=198.4, 138.3, 137.4, 133.8, 128.7, 128.4, 125.5, 26.6, 21.3. MS (EI) m/z: 134, 119, 91, 65, 51.
97%	With C₂₂H₂₀AuN₃O₂P⁽¹⁺⁾*CF₃O₃S^(1-); lithium hydroxide monohydrate; trifluoromethane sulfonic acid silver salt; glacial acetic acid at 100℃; for 10h;
97%	With lithium hydroxide monohydrate at 60℃; for 20h; Sealed tube;

96%	With 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidenegold(I) chloride In methanol; lithium hydroxide monohydrate at 110℃; for 6h; Schlenk technique; regioselective reaction;
96%	With sulfuric acid; C₁₈H₁₅CoN₂O₁₀S₂^(2-)*2Na⁽¹⁺⁾; lithium hydroxide monohydrate In methanol at 80℃; for 20h; Schlenk technique;	2.2. General procedure for hydration of terminal alkynes General procedure: The 10 mL schlenk tube was charged with phenylacetylene (0.5 mmol, 51 mg), methanol (0.625 mL), catalyst (10 μmol, 2.0%), and then H2SO4 (10 μmol, 2.0%) dissolved in H2O (2.2mmol, 0.04 mL). The mixture was heated to 80 °C and at it for 20 h in a closed tube with a magnetic stirring bar. The progres sof the reaction was monitored using TLC and GC-MS. After the reaction, the mixture was cooled to room temperature, and CH2Cl2 (5 mL) and water (5 mL) were added to the mixture.The aqueous and organic layers were separated, and the aqueous phase was extracted with CH2Cl2 (5 mL 3). The combined organic extracts were washed with a saturated NaCl solution,dried over Na2SO4, and concentrated under reduced pressure. Then the product acetophenone was obtained.
96%	With 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidenegold(I) chloride; lithium hydroxide monohydrate In methanol at 110℃; for 6h;	3 Example 3: 3-methylacetophenone The catalyst [(IPr) AuCl] (3.1mg, 0.5mol%), 3- methyl-phenylacetylene (1mmol), in methanol (1ml) and water (0.5ml) was added successively 25ml reactor.After the reaction mixture was reacted for 6 hours at 110 , cooled to room temperature.Rotary evaporation to remove the solvent, then purified by column chromatography (eluent: petroleum ether / ethyl acetate) to give pure title compound, yield: 96%
94%	With cobalt(III)((CH₂NCHC₆H₄(O))2)(OAc); sulfuric acid In methanol; lithium hydroxide monohydrate at 80℃; for 20h; Schlenk technique;
94%	With 1,3,5-cycloheptatrienylium tetrafluoroborate; lithium hydroxide monohydrate; glacial acetic acid at 130℃; for 1h; Microwave irradiation; Inert atmosphere;
92%	With lithium hydroxide monohydrate In Cyclooctan at 100℃; for 0.6h;
92%	With potassium tetrachloridoaurate(III); (S)-2-(2-(1H-benzo[d][1,2,3]triazol-1-yl)acetamido)propanoic acid; lithium hydroxide monohydrate; trifluoromethane sulfonic acid silver salt; glacial acetic acid Schlenk technique; Inert atmosphere;
91%	With trifluoromethane sulfonic acid silver salt In lithium hydroxide monohydrate; glacial acetic acid at 110℃; for 6h; Schlenk technique;	2.6 Hydration of alkynes General procedure: To a 25mL Schlenk tube, AuSBA-15 (6wt%, 20mg), AgOTf (0.05mmol) was added to a solution of phenylacetylene (1.0mmol) in HOAc/H2O (3.0mL, 15:1) under ambient air, the resulting mixture was stirred for 6hat 110°C. It was monitored by TLC. After the reaction was completed, the solvent was removed under reduced pressure and purified of the crude product by column chromatography on silica-gel afforded the desired compound.
90%	With lithium hydroxide monohydrate; trifluoromethane sulfonic acid silver salt for 7h; Heating;
90%	With indium trifluoromethanesulfonate; lithium hydroxide monohydrate; toluene-4-sulfonic acid In 1,2-dichloro-ethane for 3.5h; Sealed tube; Reflux; regioselective reaction;	6.3 4.2 General procedure for the hydration of alkynes 1a-1n and 1p-1t General procedure: The reaction mixture of In(OTf)3 (11.2 mg, 2 mol %), PTSA (57.1 mg, 30 mol %), DCE (2.0 mL), alkynes 1a-1n or 1p-1t (1.0 mmol) and water (0.2 mL) in a 10 mL flask or in a 10 mL sealed tube was stirred at reflux and monitored periodically by TLC. Upon completion, DCE was removed under reduced pressure using an aspirator, and then the residue was purified by flash chromatography (PE/EA) on silica gel to afford corresponding carbonyl compounds 2a-2n or 2p-2t.
89%	With C₂₀H₁₄AuN₂O₂⁽¹⁺⁾*Cl^(1-); lithium hydroxide monohydrate; trifluoroacetic acid In methanol at 80℃; for 5h; Sealed tube;	2.3 Typical procedure for the hydration of alkynes General procedure: Alkyne (0.5 mmol), catalyst (2.0 mol%), H2O (4.0 equiv., 0.04 mL) and CF3COOH (2.0 mol%) were dissolvedin MeOH (0.4 mL) and the homogeneous solution was stirred in a sealed tube at 80°C for 5 h. After the completion of the reaction, the mixture was cooled to room temperature, and then CH2Cl2 and H2O were added to it. The organic layer was separated and washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified over silica gel by column chromatography (25% EtOAc in hexane).
88%	With 4-methyl-morpholine; iodine In dimethyl sulfoxide at 120℃; for 16h;	Synthesis of acetophenone derivatives (2a-q) General procedure: A 10 mL reaction flask was charged with terminal alkynes 1a-q (1.0 mmol), I2 (0.3 mmol) and N-methyl morpholine (1.0 mmol) in DMSO (2.0 mL) and then the reaction mixture was heated at 120 °C for 16 h. After completion of the reaction (progress was monitored by TLC; SiO2, hexane/EtOAc = 9:1), the recation mixture was quenched with saturated sodium thiosulphate solution, diluted with water (20 mL) and extracted with ethyl acetate (3 × 15 mL). The combined organic layer was dried over anhydrous Na2SO4. Solvent was removed under reduced pressure and the remaining residue was purified over silica gel column chromatography using hexane/EtOAc = 4:1 as an eluent to obtain the desired products 2a-q in high yields.
84%	With silver hexafluoroantimonate In methanol; lithium hydroxide monohydrate at 120℃; for 24h; Sealed tube;
84%	With hydrogenchloride; lithium hydroxide monohydrate; copper chloride (I) In methanol at 20℃; for 6h; Irradiation; Inert atmosphere;	Preparation of phenylacetylene General procedure: A 10 mL reaction vessel with a magnetic stirring bar was equipped with phenylacetylene (1 mmol), CuCl (1 mol%), HCl (0.2 mL, 37 wt %) and methanol (2 mL). The mixture was irradiated with a blue LED (5 W) and stirred under at r.t. in an air atmosphere for 6 h. The distance of the reaction vial from the light is about 2 centimeter. After the reaction, the solvent was removed under reduced pressure. Purification of the crude product was achieved by flash column chromatography using petrol ether/ethyl acetate (6:1~10:1) as eluent.
82%	With lithium hydroxide monohydrate In methanol at 150℃; for 14h; Autoclave; Inert atmosphere; Green chemistry;	The general procedure of the reaction General procedure: In a 100 mL capacity of autoclave vessel a 60 mL solution of methanol and water (1:2) was added, further 1 mmol alkynes were added to this solution. The autoclave was three times purged withthe gas and then nally pressurized up to the 11 bar pressure. The reaction mixture was vigorously stirred at 150 °C for continuous 14 h. After the completion of the reaction, the reactor was cooled to room temperature, and then the argon pressure was carefully released to the atmospheric pressure. Methanol from the reaction mixture is removed using rotatory evaporator. After that, the reaction mixture was transferred in a separating funnel, and it wasworked up with ethyl acetate. The organic layer was separatedand dried over Na2SO4. Afterwards, it was filtered and concentrated under reduced pressure. The resulted crude mixture waspuried by silica gel column chromatography using ethyl acetate/n-hexane as eluent, and pure keto product was isolated.
82%	With methanol In lithium hydroxide monohydrate at -5℃; for 0.5h; Irradiation; Green chemistry;	2. Experimental General procedure: To a 100 mL capacity borosilicate immersion well of UV reactor, 80 mL aqueous methanol MeOH:H2O (1:2), alkyne (1 mmol), Rh catalyst (1.5 mol%) was added, and the reaction mixture was cooled to-5 °C. It was irradiated using a Hg vapor UV lamp, 125 W, 289 nm for30 min with continuous stirring. After completion of the reaction, the reaction mixture was left to warm to room temperature and then concentrated in vacuo. The residue was extracted with dichloromethaneand water, the organic phase was collected, dried with anhydrous Na2SO4, concentrated at reduced pressure, and puried by flash columnchromatography using hexane/ethyl acetate as eluent to obtain the corresponding product.The catalyst was synthesized as per the procedure reported in reference 15.
82%	With C₂₄H₂₀AuN₃OP⁽¹⁺⁾*F₆Sb^(1-); trifluoromethane sulfonic acid silver salt; glacial acetic acid In lithium hydroxide monohydrate at 100℃; for 12h;	1.5 Representativeprocedure for the preparation of acetophenone 8a General procedure: At room temperature, FTA-Au(I)catalyst (2 mol%), AgOTf (5 mol%) was added to a stirring solution of 6a (1.0 mmol) in HOAc/H2O(10:1, 4 mL), then the reaction mixture was heated to 100 oC andstirred overnight (12 h). After the reaction completed, the solvent was removedunder reduced pressure and the residue was purified by flash chromatography onsilica gel (ethyl acetate/hexane = 1 : 80, V/V) to give the title compound 7a in 89% yield as light yellow oil.
75%	With p-toluenesulfonic acid monohydrate; glacial acetic acid In dichloromethane at 50℃; for 3h; Sealed tube;	General procedures for alkyne hydration General procedure: The corresponding alkyne (1 mmol) was added to a solution of p-toluenesulfonic acidmonohydrate (1 mmol, 0.190 g), acetic acid (0.5 mL) in CH2Cl2 (1.0 mL). Thereaction was then sealed and stirred at the indicated temperature (oC) and for theindicated amount of times (h) in Table 2. After completion, saturated aqueousNaHCO3 (10 mL) was added to quench the reaction and then extracted with CH2Cl2(10 mL×3). The organic layer was dried over Na2SO4 and concentrated in vacuo. Theresidue was purified by column chromatography to give the pure product. Forsubstrates 1j. 1l, 1n, 1p and 1q, DCE was used as solvent in consideration ofoperation convenience.
56%	With hydrogen tetrafluoroborate In chloroform-d1; lithium hydroxide monohydrate at 60℃; for 1h;
30%	With hydrogenchloride; tetrakis-(triphenylphosphine)-palladium In tetrahydrofuran; lithium hydroxide monohydrate at 45℃; for 168h; Inert atmosphere; Schlenk technique; chemoselective reaction;
98 %Chromat.	With methanol; lithium hydroxide monohydrate; gold(I) chloride at 65℃; for 3h; Green chemistry;	General Procedure for Alkyne Hydration General procedure: In a 4 mL reaction vial equipped with a magnetic stirring bar,AuCl (5.8 mg, 0.025 mmol, 5 mol%) was added to MeOH (1 mL)under argon atmosphere. The reaction mixture was stirred for 5min, and then starting material (0.5 mmol, 1.0 equiv) and internalstandard dodecane (1.0 equiv) were added, followed bydefined amount of distilled H2O (4.0 equiv). The resulting reactionmixture was heated for 3 h, or for 24 h when needed, at65 °C. After completion of the reaction, the reaction mixturewas diluted and filtered using CH2Cl2 and injected in GC foranalysis.
	Multi-step reaction with 2 steps 1: N,N'-dibromo-4-methylbenzenesulphonamide; lithium hydroxide monohydrate / propan-2-one / 0.17 h 2: lithium hydroxide monohydrate; potassium iodide; anhydrous sodium sulphite / propan-2-one / 20 °C
99 %Chromat.	With gold(III) trichloride; lithium hydroxide monohydrate In isopropanol at 65℃; for 24h;
	With 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidenegold(I) chloride; lithium hydroxide monohydrate; trifluoromethane sulfonic acid silver salt In methanol at 120℃; for 6h;	11 N-chloro-1-m-tolylethanamine The 3-methylphenylacetylene (116 mg, 1.0 mmol), cat. [Au] (6 mg, 1 µM %), AgOTf (2.6 mg, 1 µM %), water (36 mg, 2 mmol) and methanol (1 ml) are added to the 25 mL of Claisen tube or. After closing the reaction at 120 ° C for 6 hours, cooling to room temperature. Then adding formic acid amine (315 mg, 5 mmol) and cat. [Rh] (6.2 mg, 1 mmol %), the reaction mixture in oil bath heated to 80 °C, reaction 12 hours, cooling to room temperature. Rotary evaporation of the solvent and add a certain amount of ethyl acetate and water extraction, the organic phase of the resulting product after concentrated hydrochloric acid the reflux process, rotary evaporation to remove the solvent, the final petroleum ether washing and filtering to obtain the pure target compound, yield: 89%
	With lithium hydroxide monohydrate; gold(I) chloride In dimethyl sulfoxide at 60℃;

Reference： [1]Chen, Zheng-Wang; Ye, Dong-Nai; Qian, Yi-Ping; Ye, Min; Liu, Liang-Xian [Tetrahedron, 2013, vol. 69, # 30, p. 6116 - 6120]
[2]Hu, Wenkang; Shan, Liang; Ma, Fudong; Zhang, Yilin; Yang, Yongchun; Wang, Dawei [Inorganic Chemistry Communications, 2019, vol. 109]
[3]Dong, Ying; Dong, Yu-Bin; Kan, Jing-Lan; Li, Yue; Wu, Xiaowei [Organic Letters, 2020, vol. 22, # 18, p. 7363 - 7368]
[4]Li, Feng; Wang, Nana; Lu, Lei; Zhu, Guangjun [Journal of Organic Chemistry, 2015, vol. 80, # 7, p. 3538 - 3546]
[5]Wang, Shoufeng; Miao, Chengxia; Wang, Wenfang; Lei, Ziqiang; Sun, Wei [Chinese Journal of Catalysis, 2014, vol. 35, # 10, p. 1695 - 1700]
[6]Current Patent Assignee: NANJING UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN106032348, 2016, A Location in patent: Paragraph 0028-0031
[7]Wang, Shoufeng; Miao, Chengxia; Wang, Wenfang; Lei, Ziqiang; Sun, Wei [ChemCatChem, 2014, vol. 6, # 6, p. 1612 - 1616]
[8]Oss, Giulia; Ho, Junming; Nguyen, Thanh Vinh [European Journal of Organic Chemistry, 2018, vol. 2018, # 29, p. 3974 - 3981]
[9]Location in patent: experimental part Jin, Xiongjie; Oishi, Takamichi; Yamaguchi, Kazuya; Mizuno, Noritaka [Chemistry - A European Journal, 2011, vol. 17, # 4, p. 1261 - 1267]
[10]Yang, Yongchun; Qin, Anni; Zhao, Keyan; Wang, Dawei; Shi, Xiaodong [Advanced Synthesis and Catalysis, 2016, vol. 358, # 9, p. 1433 - 1439]
[11]Huang, Ronghui; Fu, Yong; Zeng, Wei; Zhang, Liang; Wang, Dawei [Journal of Organometallic Chemistry, 2017, vol. 851, p. 46 - 51]
[12]Das, Rima; Chakraborty, Debashis [Applied Organometallic Chemistry, 2012, vol. 26, # 12, p. 722 - 726]
[13]Gao, Qi; Li, Shenyan; Pan, Yingming; Xu, Yanli; Wang, Hengshan [Tetrahedron, 2013, vol. 69, # 19, p. 3775 - 3781]
[14]Chen, Tingting; Cai, Chun [Catalysis Communications, 2015, vol. 65, p. 102 - 104]
[15]Anupam, R. O. Y.; Devi, Elangbam Pinky; Kaldhi, Dhananjaya; Malakar, Chandi C.; Saha, Indranil; Sahoo, Abhishek; Sengupta, Ragini [Asian Journal of Chemistry, 2022, vol. 34, # 6, p. 1592 - 1596]
[16]Wang, Wenlong; Zheng, Anmin; Zhao, Peiqing; Xia, Chungu; Li, Fuwei [ACS Catalysis, 2014, vol. 4, # 1, p. 321 - 327]
[17]Niu, Teng-fei; Jiang, Ding-yun; Li, Si-yuan; Shu, Xing-ge; Li, Huan; Zhang, Ai-ling; Xu, Jia-yu; Ni, Bang-qing [Tetrahedron Letters, 2017, vol. 58, # 12, p. 1156 - 1159]
[18]Ali, Munsaf; Srivastava, Avinash K.; Joshi, Raj K. [Tetrahedron Letters, 2018, vol. 59, # 21, p. 2075 - 2078]
[19]Ali, Munsaf; Srivastava, Avinash K.; Siangwata, Shepherd; Smith, Gregory S.; Joshi, Raj K. [Catalysis Communications, 2018, vol. 115, p. 78 - 81]
[20]Yao, Wei; Zhang, Yilin; Xu, Xiaqing; Yang, Yongchun; Zeng, Wei; Wang, Dawei [Journal of Organometallic Chemistry, 2019, vol. 901]
[21]Liu, Haixuan; Wei, Yunyang; Cai, Chun [Synlett, 2016, vol. 27, # 16, p. 2378 - 2383]
[22]La Sorella, Giorgio; Sperni, Laura; Ballester, Pablo; Strukul, Giorgio; Scarso, Alessandro [Catalysis science and technology, 2016, vol. 6, # 15, p. 6031 - 6036]
[23]Xu, Caixia; Du, Weiyuan; Zeng, Yi; Dai, Bin; Guo, Hao [Organic Letters, 2014, vol. 16, # 3, p. 948 - 951]
[24]Das, Atanu Kumar; Park, Sangseung; Muthaiah, Senthilkumar; Hong, Soon Hyeok [Synlett, 2015, vol. 26, # 18, p. 2517 - 2520]
[25]Rajbongshi, Kamal Krishna; Hazarika, Debojit; Phukan, Prodeep [Tetrahedron, 2016, vol. 72, # 29, p. 4151 - 4158]
[26]Schaaf, Patricia; Gojic, Vladimir; Bayer, Thomas; Rudroff, Florian; Schnürch, Michael; Mihovilovic, Marko D. [ChemCatChem, 2018, vol. 10, # 5, p. 920 - 924]
[27]Current Patent Assignee: NANJING UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN109384677, 2019, A Location in patent: Paragraph 0079-0082
[28]Mathew, Sam; Renn, Dominik; Rueping, Magnus; Sagadevan, Arunachalam [ACS Catalysis, 2021, vol. 11, # 20, p. 12565 - 12569]

42
[ 585-74-0 ]
[ 6136-68-1 ]
[ 1263183-73-8 ]
[ 41908-11-6 ]

Reference： [1]Australian Journal of Chemistry,2010,vol. 63,p. 1645 - 1655

43
[ 585-74-0 ]
[ 41908-11-6 ]

Reference： [1]Australian Journal of Chemistry,2010,vol. 63,p. 1645 - 1655

44
[ 620-14-4 ]
[ 7287-92-5 ]
[ 585-74-0 ]

Reference： [1]Journal of Molecular Catalysis A: Chemical,2012,vol. 355,p. 155 - 160

45
[ 104-94-9 ]
[ 585-74-0 ]
N-(4-methoxyphenyl)-1-(3-methylphenyl)ethylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate In neat (no solvent) at 150℃; for 24h; Molecular sieve;	4.2 Typical procedure for the direct reductiveamination of aldehydes and ketones General procedure: In a small capped-vial, aldehydes 1 or ketones 2, amines 3, and HEH were mixed together in air at different molar ratios as follows: method I: aldehydes (0.2 mmol), amines (0.24 mmol), and HEH (62 mg, 0.24 mmol); method II: aldehydes or ketones (0.27 mmol), amines (0.41 mmol), HEH (104 mg, 0.41 mmol), and 5 Å MS (0.5 g); method III: aldehydes (0.48 mmol), amines (0.16 mmol), HEH (101 mg, 0.4 mmol), and 5 Å MS (0.2 g). The reaction mixtures were heated at 150 °C without stirring. After completion of the reactions, the crude products were cooled to room temperature, dissolved in a small amount of dichloromethane, and subjected directly to the flash column chromatography to afford different kinds of the pure desired amines products 4, 5, 6, and 8.
87%	With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; S-benzyl isothiouronium chloride In toluene at 70℃; for 48h; Molecular sieve; Inert atmosphere;

Reference： [1]Nguyen, Quynh Pham Bao; Kim, Taek Hyeon [Tetrahedron, 2013, vol. 69, # 24, p. 4938 - 4943]
[2]Location in patent: experimental part Nguyen, Quynh Pham Bao; Kim, Taek Hyeon [Synthesis, 2012, vol. 44, # 13, p. 1977 - 1982]

46
[ 7287-81-2 ]
(S)-1-(3-methylphenyl)ethanol [ No CAS ]
[ 585-74-0 ]

Reference： [1]Journal of Molecular Catalysis B: Enzymatic,2012,vol. 83,p. 23 - 28

47
[ 7287-81-2 ]
[ 76-83-5 ]
[ 519-73-3 ]
[ 585-74-0 ]

Reference： [1]Organic and Biomolecular Chemistry,2013,vol. 11,p. 1978 - 1999

48
[ 1426391-53-8 ]
[ 519-73-3 ]
[ 585-74-0 ]

Yield	Reaction Conditions	Operation in experiment
1: 89% 2: 92%	With iodine In neat (no solvent) at 85℃; for 2h;

Reference： [1]Jereb, Marjan; Vrazic, Dejan [Organic and Biomolecular Chemistry, 2013, vol. 11, # 12, p. 1978 - 1999]

49
[ 70138-19-1 ]
(1R)-1-(3-methylphenyl)ethan-1-amine [ No CAS ]
[ 585-74-0 ]

Reference： [1]Chemical Communications,2013,vol. 49,p. 8629 - 8631
[2]ChemCatChem,2019,vol. 11,p. 1898 - 1902

50
potassium cyanide [ No CAS ]
[ 506-87-6 ]
[ 585-74-0 ]
[ 652992-46-6 ]

Yield	Reaction Conditions	Operation in experiment
97%	With iron(III) oxide In neat (no solvent) at 70℃; for 0.55h;	4.1 General procedure for the synthesis of 5,5-disubstituted hydantoins (4a-m) by Fe3O4 nanoparticles General procedure: In a 50-mL round-bottomed flask were poured aldehyde or ketone (1 mmol), potassium cyanide (1.3 mmol),ammonium carbonate (6 mmol), and magnetic Fe3O4nanoparticles (1 mol%) sequentially. The suspension was stirred at 70 8C in solvent-free conditions. The progress ofthe reaction was monitored by TLC (petroleum ether:ethylacetate, 1:1.2 v/v). Upon completion, the mixture was cooled to room temperature and neutralized with diluted hydrochloric acid. Then, the magnetic catalyst was removed by an external magnet and reused. The obtained product was purified by crystallization from water-ethanol. The structure of the products was characterized by comparison of their physical and spectra data with those previously reported.
97%	In ethanol; water for 0.15h; Microwave irradiation;	General Procedure for Synthesis of 5,5-Disubstituted HydantoinsUnder Conventional Heating Conditions General procedure: All of 5,5-disubstituted hydantions were synthesized by the method of Bucherer-Bergs shown in Scheme 1. Following this procedure, 5 mmol of aldehyde or ketone was dissolved in 7mL of 50% ethanol. The freshly powdered ammoniumcarbonate (2.40 g) and 0.42 g of potassium cyanide (6.5 mmol) were dissolved in 7mL H2O. The mixture was placed in a round-bottomed flask. The reactants were mixed and irradiated at microwave oven for the period as indicated in Table 1. The progress of the reaction was monitored by thin-layer chromatography (TLC, ethyl acetate=petroleum ether1:1.3 v=v). After the completion, the reaction mixture was chilled in an ice bath. The solution was neutralized with diluted hydrochloric acid. The solvent was removed under reduced pressure. The product was collected by filtrationand washed with EtOH=H2O (1:1). The product was dried and recrystallized from 95% ethanol. The products were identified by comparing their physical andspectral data with those of authentic samples.

Reference： [1]Safari, Javad; Javadian, Leila [Comptes Rendus Chimie, 2013, vol. 16, # 12, p. 1165 - 1171]
[2]Safari, Javad; Gandomi-Ravandi, Soheila; Javadian, Leila [Synthetic Communications, 2013, vol. 43, # 23, p. 3115 - 3120]

51
[ 1576-35-8 ]
[ 585-74-0 ]
[ 541533-00-0 ]

Yield	Reaction Conditions	Operation in experiment
80%	In methanol at 20℃;	Preparation of Substrates General procedure: A mixture of TsNHNH2 (3.9 g, 21 mmol) and ketone (20 mmol) in MeOH (20 mL)was stirred at room temperature. The resulting white solid was filtered, washed withMeOH and hexane, and dried in vacuo to give the corresponding N-tosyl hydrazones.
79%	In methanol Reflux;
	In methanol at 60℃;

	In methanol
	In methanol at 60℃; Inert atmosphere;	General Procedure for Preparation of Hydrazones. General procedure: To an oven dried flat-bottomed flask previously equipped with a magnetic stir bar,was charged with p-toluenesulphonohydrazide (5 mmol) in dry methanol (10 mL) at 60 °C, the ketone (5 mmol) was added drop wise. After the completion of reaction the product was began to precipitate. The crude product was filtered,washed with petroleum ether: ethyl acetate (10:1) and dried to afford the corresponding pure N-tosylhydrazones. The reaction provides the N-tosylhydrazone derivatives in about 85-98% yields.
	In methanol at 70℃;
	In methanol at 20℃;
	In methanol at 65℃;
	In methanol at 60℃; Schlenk technique;
	In methanol at 20℃; for 0.0833333h;
	In methanol at 60℃;
	In methanol at 60℃;

Reference： [1]Osako, Takao; Nagaosa, Makoto; Hamasaka, Go; Uozumi, Yasuhiro [Synlett, 2018, vol. 29, # 17, p. 2251 - 2256]
[2]Sinai, Ádám; Simkó, Dániel Cs.; Szabó, Fruzsina; Paczal, Attila; Gáti, Tamás; Bényei, Attila; Novák, Zoltán; Kotschy, András [European Journal of Organic Chemistry, 2020, vol. 2020, # 9, p. 1122 - 1128]
[3]Chen, Zhengkai; Yan, Qiangqiang; Liu, Zhanxiang; Xu, Yiming; Zhang, Yuhong [Angewandte Chemie - International Edition, 2013, vol. 52, # 50, p. 13324 - 13328][Angew. Chem., 2013, vol. 125, # 50, p. 13566 - 13570,5] Hu, Fangdong; Xia, Ying; Ye, Fei; Liu, Zhenxing; Ma, Chen; Zhang, Yan; Wang, Jianbo [Angewandte Chemie - International Edition, 2014, vol. 53, # 5, p. 1364 - 1367][Angew. Chem., 2014, vol. 126, # 5, p. 1388 - 1391,4]
[4]Cai, Zhong-Jian; Lu, Xin-Mou; Zi, You; Yang, Chao; Shen, Ling-Jie; Li, Jian; Wang, Shun-Yi; Ji, Shun-Jun [Organic Letters, 2014, vol. 16, # 19, p. 5108 - 5111]
[5]Patel, Poojan K.; Dalvadi, Jignesh P.; Chikhalia, Kishor H. [Tetrahedron Letters, 2015, vol. 56, # 47, p. 6585 - 6589]
[6]Huang, Yubing; Yu, Yue; Zhu, Zhongzhi; Zhu, Chuanle; Cen, Jinghe; Li, Xianwei; Wu, Wanqing; Jiang, Huanfeng [Journal of Organic Chemistry, 2017, vol. 82, # 14, p. 7621 - 7627]
[7]Parisotto, Stefano; Palagi, Lorenzo; Prandi, Cristina; Deagostino, Annamaria [Chemistry - A European Journal, 2018, vol. 24, # 21, p. 5484 - 5488]
[8]Deshmukh, Dewal S.; Bhanage, Bhalchandra M. [Organic and Biomolecular Chemistry, 2018, vol. 16, # 26, p. 4864 - 4873]
[9]Pang, Yue; He, Qiao; Li, Zi-Qi; Yang, Ji-Min; Yu, Jin-Han; Zhu, Shou-Fei; Zhou, Qi-Lin [Journal of the American Chemical Society, 2018, vol. 140, # 34, p. 10663 - 10668]
[10]Hu, Sipei; Du, Shiying; Yang, Zuguang; Ni, Lingfang; Chen, Zhengkai [Advanced Synthesis and Catalysis, 2019, vol. 361, # 13, p. 3124 - 3136]
[11]Reddy Lonka, Madhava; Zhang, Jinquan; Gogula, Thirupathi; Zou, Hongbin [Organic and Biomolecular Chemistry, 2019, vol. 17, # 32, p. 7455 - 7460]
[12]Baell, Jonathan B.; Feng, Jiajun; He, Tiantong; Huang, Fei; Xie, Yuxing; Yu, Yang [Organic and Biomolecular Chemistry, 2020, vol. 18, # 46, p. 9483 - 9493]

52
[ 585-74-0 ]
[ 875815-03-5 ]
[ 51012-64-7 ]

Yield	Reaction Conditions	Operation in experiment
93%	With N-Bromosuccinimide; silica gel; In methanol; for 0.25h;Reflux;	General procedure: The alpha-bromination reaction was carried out using acetophenone (1200 mg, 10 mmol), N-bromosuccinimide (2136 mg, 12 mmol), 10% (w/w) silica gel (120mg) in 10 mL of methanol at reflux conditions until the disappearance of the substrate. (Note: 2136mg of N-bromosuccinimide was added portion wise i.e. 356 mg for each time in six portions). The progress of the reaction was monitored by TLC. The reaction mass was filtered after the completion of the reaction as per TLC and the catalyst was collected for reuse. The filtrate was concentrated under vacuum. Double distilled water was added to the reaction mixture and quenched with aqueous sodium thiosulfate and the product extracted with dichloromethane (Caution: Severe burning sensation of eyes was observed during the work-up process). The layers were separated and the organic layer was collected and washed thrice with distilled water (3×50mL). The collected organic layer was dried over anhydrous Na2SO4, filtered and concentrated. The obtained crude product was purified by column chromatography over silica gel (60-120 mesh) using n-hexane-EtOAc (99:1 ratio). With the aim of studying the recycling of the catalyst, the isolated catalyst was washed with ethyl acetate (5mL) after its filtration from the reaction medium, collected and dried in vacuum at 70C to a constant weight. Subsequently it was reused for the alpha-bromination of acetophenone and achieved 95%, 86% and 83% yields of product (2a) for first, second and third reuse of catalyst respectively. All products gave spectroscopic data in agreement with the literature [15,21,27-30]. The method is also very practical for scale up in process development. We attempted large scale (100 gram scale) synthesis of 2-bromo-1-phenylethanone 2a and obtained fruitful results with isolated yields ranging from 93% to 96%.

Reference： [1]Chinese Chemical Letters,2014,vol. 25,p. 179 - 182

53
[ 1527-91-9 ]
[ 585-74-0 ]
[ 1610784-77-4 ]

Yield	Reaction Conditions	Operation in experiment
81%	With 1,10-Phenanthroline; copper diacetate; aniline; lithium bromide; zinc(II) iodide; In 1,2-dichloro-benzene; at 120.0℃; for 2.0h;Green chemistry;	General procedure: Synthesis of 1,2,4-triphenyl-1H-imidazole (3a): the reaction was carried out in a round-bottom sidearm flask (10 mL), 1a (0.24 mmol), 2a (0.2 mmol), Cu(OAc)2 (10 mol %), ZnI2 (10 mol %), aniline (5 mol %), 1,10-phenanthroline (20 mol %), LiBr(3.0 equiv) and DCB (2 mL) were added to the flask with a magnetic stirring bar at 120 C under air. After 6 h stirring at this temperature,the flask was took out and cooled to room temperature. The mixture was filtered with ethyl acetate (350 mL), and the filtrate was concentrated under reduced pressure to distill ethyl acetate. Subsequently, the crude product with DCB was dried under heat gun, which was further purified by silica gel chromatography (petroleum/ethyl acetate10:1 as eluent) to obtain product 3a.

Reference： [1]Tetrahedron,2014,vol. 70,p. 4038 - 4042

54
[ 95-16-9 ]
[ 585-74-0 ]
[ 804549-56-2 ]

Yield	Reaction Conditions	Operation in experiment
91%	With tert.-butylhydroperoxide; iodine In water monomer; dimethyl sulfoxide at 60℃; for 3h;	Benzo[d]thiazol-2-arylmethanones 3; General Procedure General procedure: A mixture of benzothiazole 1 (0.4 mmol), aryl ketone 2 (0.4 mmol), I2 (0.4 mmol) and TBHP (70%, 1.2 mmol) was heated at 60 °C in DMSO for 3 h. After completion of the reaction, EtOAc and saturated aqueous Na2S2O3 solution were added. The organic layer was separated, dried (MgSO4), filtered and evaporated under reduced pressure. The crude residue was purified by flash chromatography (silica gel, petroleum ether/ethyl acetate, 25:1 to 8:1) to give product 3a-t.
83%	With copper (I) iodide; hydrogen tetrafluoroborate In water monomer; dimethyl sulfoxide at 130℃; for 9h; Inert atmosphere; Sealed tube; chemoselective reaction;
83%	With bis-[(trifluoroacetoxy)iodo]benzene; potassium hydroxide In water monomer; dimethyl sulfoxide at 85℃; for 10h;	4.2. Synthesis General procedure: A mixture of 2H-benzothiazole 1 (0.45 mmol), aryl methyl ketone 2 (0.30 mmol), KOH (1 equiv., 0.30 mmol), and PIFA (2 equiv., 0.60 mmol) was heated at 85 °C in DMSO/H2O(v/v, 3/1, 2 mL) for 10 h. After cooling to room temperature, the reaction mixture was diluted with H2O (30 mL) and extracted with dichloromethane (3 10 mL). The combined organic layers were then dried over anhydrous Na2SO4, filtered, and concentrated under vacuum. The resulting residue was purified by column chromatography (silica gel,petroleum ether/ethyl acetate, 20:1 to 8:1) to give products 3aa-3bs.

83%

With bis-[(trifluoroacetoxy)iodo]benzene; potassium hydroxide In water monomer; dimethyl sulfoxide at 85℃; for 10h;

4.2. Synthesis General procedure: A mixture of 2H-benzothiazole 1 (0.45 mmol), aryl methyl ketone 2 (0.30 mmol), KOH (1 equiv., 0.30 mmol), and PIFA (2 equiv., 0.60 mmol) was heated at 85 °C in DMSO/H2O(v/v, 3/1, 2 mL) for 10 h. After cooling to room temperature, the reaction mixture was diluted with H2O (30 mL) and extracted with dichloromethane (3 10 mL). The combined organic layers were then dried over anhydrous Na2SO4, filtered, and concentrated under vacuum. The resulting residue was purified by column chromatography (silica gel,petroleum ether/ethyl acetate, 20:1 to 8:1) to give products 3aa-3bs.

Reference： [1]Wang, Bin; Zhang, Qianwei; Guo, Zhongqi; Ablajan, Keyume [Synthesis, 2020, vol. 52, # 2, p. 3058 - 3064]
[2]Feng, Qiang; Song, Qiuling [Advanced Synthesis and Catalysis, 2014, vol. 356, # 11-12, p. 2445 - 2452]
[3]Hu, Zhi-Gang; Huang, Zhen; Sun, Xiao-Tong; Weng, Jian-Quan; Zhou, Ling-Li [Molecules, 2022, vol. 27, # 3]
[4]Hu, Zhi-Gang; Huang, Zhen; Sun, Xiao-Tong; Weng, Jian-Quan; Zhou, Ling-Li [Molecules, 2022, vol. 27, # 3]

55
[ 3392-97-0 ]
[ 585-74-0 ]
(E)-1-(3-methylphenyl)-3-(2,6-dimethoxyphenyl)prop-2-en-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%		General procedure: A 50 mL flask was charged with substituted acetophenone (5 mmol) and a solution of sodium hydroxide (10 mmol) in a 4:1 (v/v) mixture of ethanol/H2O (25 mL), and the resulting mixture was stirred at room temperature for 5 min. A substituted benzaldehyde (5 mmol) was then added to the reaction, and the resulting mixture was stirred at room temperature. The reaction was then monitored byTLC using ethyl acetate/petroleum ether (1:4 or 1:2 v/v) as the solvent system. Upon completion of the reaction, the crude product was filtered off and recrystallized from a mixture of dichloromethane and ethanol or purified by column chromatography over silica gel eluting with a mixture of petroleum ether and ethyl acetate to give the pure product.

Reference： [1]Molecules,2014,vol. 19,p. 17256 - 17278

56
[ 585-74-0 ]
[ 1630984-18-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: titanium(IV) tetraethanolate / tetrahydrofuran / 16 h / 60 °C 2: L-Selectride / tetrahydrofuran / -78 - 0 °C / Inert atmosphere 3: acetyl chloride / ethanol / 2 h / 20 °C

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2014/205223, 2014, A1

57
[ 585-74-0 ]
[ 138457-18-8 ]

Reference： [1]Patent: WO2014/205223,2014,A1

58
[ 123-75-1 ]
[ 13292-22-3 ]
[ 585-74-0 ]
3-[3-(3-methylphenyl)-3-(pyrrolidine-1-ylidenium)prop-1-ene-1-yl]rifamycine-SV-8-olate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78.3%	With acetic acid; In methanol; at 45 - 50℃; for 1h;	0.8 g of <strong>[13292-22-3]<strong>[13292-22-3]3-formylrifamycin</strong> SV</strong> (1) (1 mmol) was added to a solution containing: 15.0 ml of methanol, 0.3 g of acetic acid, 0.36 g (5mmol) of pyrrolidine and 1.35 g (10 mmol) of 3-methylacetophenone. The system was stirred at 45-50C for 1.0 h. The crystalline blue product was separated according to 7.2. 0.70 g of 9 was obtained. Yield 78.3%. MS (ESI): m/z (%): 917,4 (100.0), [M+Na]+; 895.4 (93.4) [M+H]+. HRMS calcd for [M+H]+ C51H63N2O12 895.43755, found 895.43769 (error: 0.15ppm). IR: 3439, 2973, 1730, 1664, 1564, 1512, 1480, 1236cm-1.

Reference： [1]Tetrahedron,2015,vol. 71,p. 158 - 169

59
[ 5813-86-5 ]
[ 585-74-0 ]
3-methoxy-N-[2-oxo-2-(m-tolyl)acetyl]benzamide [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2015,vol. 2015,p. 3577 - 3586

60
[ 585-74-0 ]
1,3-bis(3-methylphenyl)butan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	With acetylacetonatodicarbonylrhodium(l); hydrogen; iodine; 1,4-di(diphenylphosphino)-butane In 1,2-dichloro-ethane at 20 - 50℃; for 72h; Schlenk technique; Glovebox;	General procedure for the synthesis of 2a General procedure: General procedure for the synthesis of 2a-2m. Rh(CO)2(acac) (0.01 mmol), dppb (0.012 mol) and 1 mL of DCE were added to a Schlenk tube under an argon atmosphere in a glovebox. The mixture was stirred at room temperature for 30 min. Then acetophenone 1a-1m (0.4 mmol) and iodine (0.3 mmol) were added. The reaction mixture was stirred in a hydrogen atmosphere at rt or 50 °C for 72 h. After vacuum evaporation of the solvent, the residue was purified by silica gel column chromatography to provide the desired product 2a-2m.
46%	With hydrogen iodide at 25℃; for 48h; Inert atmosphere;	general procedure forthe formation of α-alkylated product. General procedure: In a 50 mL round bottom flask fitted with a three-way cock with a septum was placed acetophenone (0.121 g, 1.01 mmol). The flask was filled with nitrogen after reducing pressure. After a slight decompression to ease the introduction of gas, HI gas (0.136 g, 1.06 mmol) was put into the vessel with a syringe through the septum (the weight of HI gas was calculated with the change in the weight of the equipment both before and after the introduction of HI gas). gas was introduced And nitrogen into the vessel to release the difference in pressure against the atmosphere. The mixture stood at 25 °C for 2 d. After reducing the pressure to release HI gas, saturated Na2S2O3 (20 mL) and brine(15 mL) was added to the reaction mixture. After being extracted with CHCl3(15 mL × 3), the organic layer was dried with MgSO4. After concentration, the residue (90.7 mg) was obtained. 7.4 mg of the residue was combined with p-chlorobenzaldehyde(7.4 mg) as an internal standard. The mixture was then measured with 1H NMR to determine the yield via the integration of a methyl peak of 3-methyl-1,3-diphenylpropan-1-one (1.34 ppm) and formyl peak of p-chlorobenzaldehyde (9.98 ppm) (integration ratio = 1.0 : 1.61,69% yield estimated by the formation of one product molecule by two starting molecules).Furthermore, the reaction mixture included in p-chlorobenzaldehyde was subjected to column chromatography on SiO2(hexane : EtOAc = 8 : 1) to give 3-methyl-1,3-diphenylpropan-1-one (67.7 mg, 0.302 mmol, 60%) as a colorless solid:

Reference： [1]Li, Sida; Laishram, Ronibala Devi; Shen, Guoli; Zhang, Xuexin; Yang, Yong; Ni, Jianxiao; Zhan, Yong; Zhou, Yongyun; Fan, Baomin [Synthetic Communications, 2020, vol. 50, # 12, p. 1790 - 1798]
[2]Matsumoto, Shoji; Koitabashi, Seigo; Otani, Yasuhiko; Akazome, Motohiro [Tetrahedron Letters, 2015, vol. 56, # 29, p. 4320 - 4323]

61
[ 2835-06-5 ]
[ 585-74-0 ]
5-(3-methylphenyl)-2-phenyloxazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With iodine; 4-aminobenzene sulfonic acid In dimethyl sulfoxide at 100℃; for 5h;	Typical Procedure for the Preparation of 2,5-Diphenyloxazole General procedure: A test tube was charged with 1a (0.32 mmol), 2a (0.38 mmol), I2 (2.0 equiv.) and PABS (0.5equiv.). Then 2 mL DMSO was added to the reaction system. The reaction was stirred at 100 oCfor 5 h. After cooling to room temperature, the solvent diluted with 10 mL ethyl acetate andwashed with 5 mL brine and dried over anhydrous Na2SO4. After the solvent was evaporated invacuo, the residues were purified by column chromatography, eluting with petroleum ether/EtOAc to afford pure 3aa.

Reference： [1]Hu, Ting; Yan, Hao; Liu, Xingxing; Wu, Chaoyang; Fan, Yuxing; Huang, Jing; Huang, Guosheng [Synlett, 2015, vol. 26, # 20, p. 2866 - 2869]

62
[ 99-36-5 ]
[ 585-74-0 ]
[ 59826-44-7 ]

Yield	Reaction Conditions	Operation in experiment
63%	With sodium hydride In toluene Inert atmosphere; Reflux;
	Stage #1: 3-Methylacetophenone With sodium hydride In tetrahydrofuran at 0℃; for 1h; Stage #2: 1-methoxycarbonyl-3-methylbenzene In tetrahydrofuran at 0 - 20℃;
	Stage #1: 3-Methylacetophenone With sodium hydride In tetrahydrofuran at 0℃; for 1h; Stage #2: 1-methoxycarbonyl-3-methylbenzene In tetrahydrofuran at 25℃;

With sodium hydride In tetrahydrofuran at 0 - 20℃; for 4h; Inert atmosphere;

Reference： [1]Beck, Thorsten M.; Breit, Bernhard [Organic Letters, 2016, vol. 18, # 1, p. 124 - 127]
[2]Qian, Jinlong; Yi, Wenbin; Huang, Xin; Jasinski, Jerry P.; Zhang, Wei [Advanced Synthesis and Catalysis, 2016, vol. 358, # 17, p. 2811 - 2816]
[3]Biswas, Rayhan G.; Ray, Sumit K.; Unhale, Rajshekhar A.; Singh, Vinod K. [Organic Letters, 2021, vol. 23, # 16, p. 6504 - 6509]
[4]Sadhu, Milon M.; Ray, Sumit K.; Unhale, Rajshekhar A.; Singh, Vinod K. [Organic and Biomolecular Chemistry, 2022, vol. 20, # 2, p. 410 - 414]

63
[ 585-74-0 ]
2-azido-1-m-tolylethanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: 3-Methylacetophenone With N-Bromosuccinimide; toluene-4-sulfonic acid In acetonitrile at 0℃; for 1h; Reflux; Stage #2: With Caswell No_. 744A In acetonitrile at 20℃; for 4h;	General Procedure for the Synthesis of Azides of Substituted Acetophenones 8-23 General procedure: Round Bottom Flask was charged with substituted acetophenone (6.5 mmol) in acetonitrile (20 mL) at 0 °C. Then p-TsOH (9.7 mmol) and NBS (9.0 mmol) were added and resulting mixture was refluxed for an hour. After that, mixture was cooled to room temperature and sodium azide (19.4 mmol) was added to the stirred solution for 4 h. Upon completion, cold water was added to the reaction mixture and extracted with EtOAc (2*20 mL). The organic layers were then dried using anhydrous MgSO4, filtered and concentrated. The crude product was purified via column chromatography using 5-10% ethyl acetate in n-hexanes as a solvent system, to obtain corresponding azides 823 in 20-79% yield.
	Stage #1: 3-Methylacetophenone With N-Bromosuccinimide; toluene-4-sulfonic acid In acetonitrile for 1h; Reflux; Stage #2: With Caswell No_. 744A at 20℃; for 4h;
	Stage #1: 3-Methylacetophenone With N-Bromosuccinimide; toluene-4-sulfonic acid In acetonitrile for 1h; Reflux; Stage #2: With Caswell No_. 744A In acetonitrile at 20℃; for 4h;

Reference： [1]Khan, Maria Aqeel; Saleem, Aliyan; Ghouri, Nida; Hameed, Abdul; Iqbal Choudhary; Basha, Fatima Z. [Letters in drug design and discovery, 2015, vol. 12, # 7, p. 597 - 606]
[2]Khan, Maria A.; Javaid, Kulsoom; Batool, Farhana; Basha, Fatima Z.; Choudhary, Muhammad I.; Wadood, Abdul; Jamal, Alam; Fazal-Ur-Rehman, Saba [Medicinal Chemistry, 2017, vol. 13, # 7, p. 698 - 704]
[3]Basha, Fatima Z.; Batool, Farhana; Ganatra, Muhammad Uzair; Iqbal, Shazia; Jabeen, Almas; Khan, Maria A.; Yousuf, Sammer; Zafar, Fatima [Journal of Molecular Structure, 2022, vol. 1261]

64
[ 119-67-5 ]
[ 585-74-0 ]
3-(3-methylphenyl-2-oxoethyl)isobenzofuran-1(3H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With ziconium(IV) oxychloride octahydrate In neat (no solvent) at 140℃; for 3h; Sealed tube;	Syntheis of3-(2-phenyl-2-oxoethyl)isobenzofuran-1(3H)-one (1) General procedure: Acetophenone (144 mL, 1.20 mmol), phthalaldehydic acid (150 mg,1.00 mmol) and ZrOCl2×8H2O (32.0 mg, 0.100 mmol) wereplaced in a sealed tube. The mixture was heated at 140 oC for 3hours. The progress of the reaction was monitored by TLC. After completion ofthe reaction, the residue was submitted to purification by columnchromatography (hexane/ethyl acetate 3:1 v/v). Pure 3-(2-phenyl-2-oxoethyl)isobenzofuran-1(3H)-one (1) was obtained after recrystallizationusing EtOH-water 2:1 v/v.By using this procedure, compound 1was obtained in 91% yield (230 mg, 0.910 mmol).
56%	With sodium hydroxide In ethanol for 4h;	3.2. General Procedure for the Synthesis of 3-(2-Oxo-2-phenylethyl)isobenzofuran-1(3H)-ones 4a-4m General procedure: To a stirred solution of 2-carboxybenzaldehyde (15.0 g; 0.1 mol) dissolved in ethanol (50 mL)in a 1 L three-necked round bottom flask was added the relevant acetophenone (0.1 mol). The flaskwas immersed in a bath of crushed ice. Sodium hydroxide (75 mL, 1.75 M) was added dropwiseand the mixture was stirred mechanically for 4 h. The resulting mixture was neutralized withdilute hydrochloric acid. Diethyl ether (approximately 50 mL) was added to precipitate the product.The crude product was filtered, washed with a small volume of distilled water and recrystallized fromdichloromethane and ethanol.

Reference： [1]Da Silva Maia, Angélica Faleiros; Siqueira, Raoni Pais; De Oliveira, Fabrício Marques; Ferreira, Joana Gasperazzo; Da Silva, Silma Francielle; Caiuby, Clarice Alves Dale; De Oliveira, Leandro Licursi; De Paula, Sérgio Oliveira; Souza, Rafael Aparecido Carvalho; Guilardi, Silvana; Bressan, Gustavo Costa; Teixeira, Róbson Ricardo [Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 12, p. 2810 - 2816]
[2]Bassin, Jatinder P.; Anagani, Bhavani; Benham, Christopher; Goyal, Madhu; Hashemian, Maryam; Gerhard, Ute [Molecules, 2016, vol. 21, # 8]

65
[ 4098-06-0 ]
[ 585-74-0 ]
1-((4,6-di-O-acetyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl)-1-(3-methylphenyl)ethanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	Stage #1: 3-Methylacetophenone With t-butyldimethylsiyl triflate; N-ethyl-N,N-diisopropylamine In dichloromethane for 0.333333h; Inert atmosphere; Stage #2: triacetyl-D-galactal In dichloromethane at 0 - 30℃; Inert atmosphere;	(I) General information for the synthesis of glucopyranoside. General procedure: To an oven-dried 10-mL round-bottomed flask under N2 wasadded CH2Cl2 (5.0 mL), Acetophenone/chromanone (1.0 mmol,200 mg), iPr2NEt (234 mL, 1.20 mmol), TBSOTf (324 mL 1.25 mmol).After 20 min, protected sugar (1.1 mmol 335 mg) was added at 0 C,and the mixture was stirred at room temperature for the indicatedtime. The reaction mixture was passed through a silica gel plug(1 cm 5 cm) with Et2O and was neutralized by aqueous NaHCO3solution. The Et2O extract was removed by rotary evaporation. Theproduct was purified by silica gel chromatography (10e15% EtOAc/hexanes) from which only the major product was isolated. Thespectral data of representative compounds are shown below.

Reference： [1]Dash, Ashutosh K.; Madhubabu, Tatina; Yousuf, Syed Khalid; Raina, Sushil; Mukherjee, Debaraj [Carbohydrate Research, 2017, vol. 438, p. 1 - 8]

66
[ 2265-91-0 ]
[ 585-74-0 ]
1-(3′,5′-difluoro-4-methyl-[1,1′-biphenyl]-2-yl)ethanone [ No CAS ]

Reference： [1]Organic Letters,2017,vol. 19,p. 1562 - 1565

67
[ 7287-81-2 ]
(1R)-1-(3-methylphenyl)ethan-1-amine [ No CAS ]
[ 585-74-0 ]

Reference： [1]Organic and Biomolecular Chemistry,2017,vol. 15,p. 8313 - 8325

68
[ 104-94-9 ]
[ 585-74-0 ]
[ 434951-37-8 ]

Yield	Reaction Conditions	Operation in experiment
87%	With Hβ zeolite In toluene at 120℃; for 24h; Sealed tube; Green chemistry;	2.2 General Procedure General procedure: Hβ zeolite (100mg) was added to the well stirred solutionof aromatic ketone (2mmol), aniline (2mmol) and toluene(1mL) in a 15mL sealed tube and the reaction mixturewas allowed to stir at 120°C. After 24h, the reaction mixturewas cooled to room temperature and diluted with ethylacetate (10mL). The catalyst was separated by simple fltrationand the exclusion of solvent in vacuo yielded the crudewhich was further purified by column chromatography usingsilica gel (100-200 mesh) to afford pure products. All theproducts were identified on the basis of 1H and 13C NMRspectral data.
	With toluene-4-sulfonic acid In benzene for 10h; Dean-Stark; Reflux;
	With toluene-4-sulfonic acid for 10h; Reflux; Dean-Stark;

In benzene for 72h; Molecular sieve; Inert atmosphere;

Reference： [1]Amrutham, Vasu; Mameda, Naresh; Kodumuri, Srujana; Chevella, Durgaiah; Banothu, Rammurthy; Gajula, Krishna Sai; Grigor’eva, Nellya Gennadievna; Nama, Narender [Catalysis Letters, 2017, vol. 147, # 12, p. 2982 - 2986]
[2]Zhu, Chengfeng; Luan, Jichao; Fang, Jun; Zhao, Xu; Wu, Xiang; Li, Yougui; Luo, Yunfei [Organic Letters, 2018]
[3]Zhu, Chengfeng; Luan, Jichao; Fang, Jun; Zhao, Xu; Wu, Xiang; Li, Yougui; Luo, Yunfei [Organic Letters, 2018, vol. 20, # 18, p. 5960 - 5963]
[4]Akiyama, Takahiko; Ito, Yui; Miyashita, Hiromitsu; Saito, Kodai; Yamanaka, Masahiro [Organic Letters, 2020]

69
[ 585-74-0 ]
[ 74-88-4 ]
[ 5208-37-7 ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: methyl iodide With magnesium In diethyl ether at 0 - 20℃; for 1.5h; Stage #2: 3-Methylacetophenone In diethyl ether at 0 - 20℃; for 12h; Stage #3: With ammonium chloride In diethyl ether; water	3.1.1. 2-(4-Tolyl)propan-2-ol (1g) General procedure: To a suspension of Mg (turnings) (0.293 g, 12.1 atom) in anhy-drous Et2O (17.5 mL) was dropwise added MeI (1.90 g,13.4 mmol) at0C. The suspension was stirred for 1.5 h at room temperature untilMg was disappeared. To the solution was dropwise added 4-methylacetophenone (1.36 g, 10.1 mmol) at 0C, and the mixturewas stirred for 12 h at room temperature. To the reaction mixturewas added H2O (25 mL) and saturated aqueous NH4Cl (25 mL). Afterbeing extracted with EtOAc (30 mL 3), the organic layer was driedwith MgSO4. After the concentration, 2-(4-tolyl)proan-2-ol (1.44 g,9.55 mmol) was obtained in 94% yield as colorless oil.
	Stage #1: methyl iodide With magnesium In diethyl ether for 1h; Inert atmosphere; Reflux; Stage #2: 3-Methylacetophenone In diethyl ether at 0 - 5℃;
	Stage #1: methyl iodide With iodine; magnesium In diethyl ether for 1h; Inert atmosphere; Reflux; Stage #2: 3-Methylacetophenone In diethyl ether at 0 - 5℃; Inert atmosphere;

Reference： [1]Matsumoto, Shoji; Naito, Masafumi; Oseki, Takehisa; Akazome, Motohiro; Otani, Yasuhiko [Tetrahedron, 2017, vol. 73, # 52, p. 7254 - 7259]
[2]Kapoor, Mohit; Chand-Thakuri, Pratibha; Young, Michael C. [Journal of the American Chemical Society, 2019, vol. 141, # 19, p. 7980 - 7989]
[3]Chand-Thakuri, Pratibha; Landge, Vinod G.; Kapoor, Mohit; Young, Michael C. [Journal of Organic Chemistry, 2020, vol. 85, # 10, p. 6626 - 6644]

70
[ 132838-25-6 ]
[ 585-74-0 ]
(E)-3-(3-(2-fluoroethoxy)phenyl)-1-(3-methylphenyl)prop-2-en-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With potassium hydroxide In ethanol; water at 20℃; for 0.5h;	3.5. General Procedure for the Preparation of Fluoroethoxychalcones General procedure: An aqueous solution of KOH (1.2 eq.) was added at room temperature to a solution of the appropriate acetophenone (1.0 eq.), and benzaldehyde (1.2 eq.) in ethanol (10 mL). The reaction mixture was then stirred for 30 min. After completion of reaction, the reaction was judged by TLC. The reaction mixture was filtered through a Buckner funnel under vacuum. The solid was washed several times with a 1:1 ethanol-water mixture. The solid was finally dried under vacuum. The crude product was further purified by column chromatography or recrystallization.

Reference： [1]Devi, Kavita; Rajendran, Vinoth; Ayushee; Rangarajan; Singh, Rishi Pal; Ghosh, Prahlad C.; Singh, Manjula [Molecules, 2018, vol. 23, # 5]

71
[ 667-27-6 ]
[ 585-74-0 ]
ethyl 2-(4-acetyl-2-methylphenyl)-2,2-difluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium acetate; silver fluoride; triphenylphosphine In hexane at 140℃; for 20h; Sealed tube; Inert atmosphere;	5.1-5.3 In this embodiment, a preparation method of a benzoyl para-difluoroalkylated derivative is shown as follows: 3-methylacetophenone is used as a raw material, and the reaction formula is as follows: (1) 3-methylacetophenone 0.0268 g (0.2 mmol) and tetrakistriphenylphosphine palladium 0.0116 g were added to the reaction tube.(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 74%).
74%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium acetate; silver fluoride; triphenylphosphine In hexane at 140℃; for 20h; Inert atmosphere; Sealed tube;
62%	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; (2S,3S)-N-acetyl-2-amino-3-methylpentanoic acid; silver trifluoroacetate; sodium carbonate; <i>tert</i>-butylamine In 1,2-dichloro-ethane at 155℃; for 36h; Inert atmosphere; regioselective reaction;	General Experimental Procedure for the Synthesis of Corresponding Products General procedure: Mixture of 1 (0.2 mmol, 1.0 equiv), 2 (0.6 mmol, 3.0 equiv), [Ru(p-cymene)Cl2]2 (6.1 mg, 5 mol%), Na2CO3 (42.4 mg, 2.0 equiv), AgTFA (88.3 mg, 2.0 equiv), N-acetyl-L-isoleucine (10.3 mg, 30 mol%), 2-methylpropan-2-amine (11 μL, 0.5 equiv) and DCE (1.0 mL) in a reaction tube (15 mL) under argon atmosphere was heated at 155 °C for 36 hours. Upon completion, the reaction mixture was cooled to ambient temperature, filtered through a silica gel plug, and concentrated in vacuo. The crude reaction mixture was purified on silica gel using hexanes/EtOAc as the eluent to afford the desired product.

54%

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;

Reference： [1]Current Patent Assignee: SOOCHOW UNIVERSITY (SUZHOU) - CN108586251, 2018, A Location in patent: Paragraph 0058-0063
[2]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]
[3]Cheng, Yaohang; He, Yuhang; Zheng, Jie; Yang, Hui; Liu, Jun; An, Guanghui; Li, Guangming [Chinese Chemical Letters, 2021, vol. 32, # 4, p. 1437 - 1441]
[4]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]

72
[ 3393-45-1 ]
[ 585-74-0 ]
C₁₄H₁₈O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	Stage #1: 5,6-dihydro-pyran-2-one; 3-Methylacetophenone With tetrakis(actonitrile)copper(I) hexafluorophosphate; (R,Rp)-1-(2-(diphenylphosphino)ferrocenyl)-1-(2-diphenylphosphinophenyl)-N,N-dimethylmethanamine; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate; isopropyl alcohol; bis(pinacol)diborane; sodium t-butanolate In tetrahydrofuran at -50℃; for 36h; Schlenk technique; Glovebox; Inert atmosphere; Stage #2: With sodium perborate tetrahydrate In tetrahydrofuran; water at 25℃; for 3h; Schlenk technique; Glovebox; Inert atmosphere; enantioselective reaction;	4.1. Typical experimental procedure General procedure: To a dried 25 mL Schlenk tube equipped with a magnetic stirring bar were charged with Cu(CH3CN)4PF6 (3.7 mg, 0.01 mmol, 5.0 mol %), NaBArF (8.8 mg, 0.01 mmol, 5.0 mol %), NaOtBu (28.8 mg, 0.30 mmol, 1.5 equiv) and (R,Rp)-TANIAPHOS (8.3 mg, 0.012 mmol, 6.0 mol %) in a glove box under Ar atmosphere. Anhydrous THF (2.0 mL, 0.1 M) was added via a syringe. The mixture was stirred at 25 °C for 30 min. Then bis(pinacolato)diboron (76.0 mg, 0.30 mmol, 1.5 equiv) was added to the solution. The mixture was allowed to stir at 25 °C for 10 min under N2 atmosphere. After the reaction mixture was cooled to 50 °C, 2-Acetonaphthone 1a (51 mg, 0.30 mmol, 1.5 equiv) and 5,6-Dihydro-2H-pyran-2-one 2 (18mL, 0.20 mmol, 1.0 equiv) were added. The resulting mixture was stirred at 50 °C for 36 h before the reaction was quenched by 2 mL saturated ammonium chloride water solution. Then, NaBO3*4H2O (154.0 mg, 1.0 mmol, 5.0 equiv) was added and the resulting mixture was allowed to stir at 25 °C for three hours. The aqueous layer was extracted with Et2O (2 mL x 3). The combined organic layers were concentrated in vacuo to provide brown oil, which was purified by silica gel chromatography (petroleum ether: ethyl acetate = 2:1) to afford 34.9 mg 4a as white solid (61% yield).

Reference： [1]Zhang, Qi; Jia, Xueshun; Yin, Liang [Tetrahedron, 2019, vol. 75, # 12, p. 1676 - 1681]

73
[ 37585-16-3 ]
[ 585-74-0 ]
7-chloro-2-(3'-methylphenyl)quinoline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With tris(triphenylphosphine)ruthenium(II) chloride; potassium hydroxide; In toluene;Reflux;	23.4 g (148.4 mmol) of <strong>[37585-16-3]2-amino-4-chloro-benzyl alcohol</strong>, 29.9 g of 3'-methylacetophenone(222.7 mmol), 2.8 g of tris(triphenylphosphine)ruthenium (II) chloride, and 9.2 g of potassium hydroxide and 180 mL of toluene were placed in a reaction flask, stirred under heating to reflux, and separated by a condensed reflux water separator. When the reaction was completed, it was cooled to room temperature and the pad was filtered through silica gel. The product was further purified by column chromatography (eluent: n-hexane / ethyl acetate = 2 / 100), and finally crystallised from isopropanol to give 22.6 g of 7-chloro-2-(3'-methylphenyl)quinoline ( Yield: 60.0%).

Reference： [1]Patent: CN108997437,2018,A .Location in patent: Paragraph 0044; 0045; 0046

74
[ 70138-19-1 ]
[ 138457-18-8 ]
[ 585-74-0 ]

Reference： [1]ChemCatChem,2019,vol. 11,p. 1898 - 1902

75
[ 400-38-4 ]
[ 585-74-0 ]
[ 53764-99-1 ]

Yield	Reaction Conditions	Operation in experiment
87%	With sodium methylate; In toluene; for 4h;Reflux;	To a solution of isopropyl 2,2,2-trifluoroacetate 10 (7.40g, 0.0474mol) in toluene (15 mL) was added and 3?-methylacetophenone 11 (6.36g, 0.0474mol) and cooled to 0C, followed by dropwise addition Sodium methoxide (3.0g, 0.0616 mol) to the reaction mixture. The reaction mixture was heated to reflux. After stirring for 4 h, the reaction mixture was diluted with water (275 mL), brine (275 mL), EtOAc (500 mL). The aqueous layer was separated and extracted with EtOAc (200 mL x 4). The combined organic phases were washed with brine (500 mL x 1), dried over Na2SO4 and concentrated under vacuum. The crude product purified by flash column chromatography to give 4,4,4-trifluoro-1-(m-tolyl)butane-1,3-dione, 8 as a white solid (9.5g, 87% yield). To a 500 mL round-bottomed flask containing ethyl acetate (20 mL) and water (16 mL) was added 4,4,4-trifluoro-1-(m-tolyl)butane-1,3-dione 8 (4.0g, 0.0174mol), the reaction mixture was cooled to 0C and stirred for 15 min. 4-hydrazinobenzenesulfonamide hydrochloride7 (4.0g, 0.0214 mol) was added to the reaction mixture slowly. The reaction was refluxed for 8 h then cooled to rt. The solid precipitated on cooling was filtered, the filtered solid was washed with cold isopropyl alcohol (20mL X 2) to give the the impurity A 2 as white solid (5.15g) with an excellent yield of 92.0%. 4-(5-(m-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)benzenesulfonamide (2) 1H NMR (400 MHz, DMSO - d6) delta 7.94 - 7.79 (m, 2H), 7.60 - 7.45 (m, 4H), 7.21 (dd, J = 10.9, 5.1 Hz, 4H), 7.08 - 6.89 (m, 1H), 2.25 (s, 3H). 13C NMR(101 MHz, DMSO - d6) delta 145.82, 144.54, 142.86, 142.45, 141.59, 138.80, 130.57, 130.04, 129.18, 128.69, 127.31, 126.51, 121.86 (q, J = 265 Hz), 106.91, 21.42. 19F NMR (376 MHz, DMSO - d6) delta -60.77. HRMS m/z (M-H)-: 380.0695; calculated for C17H14F3N3O2S; 380.0686

Reference： [1]Bulletin of the Korean Chemical Society,2019,vol. 40,p. 479 - 480

76
[ 585-74-0 ]
[ 51015-29-3 ]

Reference： [1]Journal of Heterocyclic Chemistry,2019,vol. 56,p. 1672 - 1683

77
[ 17356-08-0 ]
[ 585-74-0 ]
5,5'-thiobis(4-(m-tolyl)thiazol-2-amine) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With iodine In dimethyl sulfoxide at 40℃; for 5h; Green chemistry;	2.3. General procedure for the synthesis of diheteroaryl thioethers General procedure: A mixture of methyl ketone (1 mmol), thiourea (2 mmol), iodine(1 mmol), and Arg-SNP (0.02 g) was stirred at 40°C in DMSO solvent.After the completion of reaction (monitored by TLC; hexane/AcOEt 1:1), the bio-heterogeneous nanocatalyst was separated byfiltration and the organic layer was extracted with saturated sodiumthiosulfate/water and ethyl acetate solution. the solvent wasremoved under reduced pressure. The pure product was recrystallizedby hot ethanol in high yield. All diheteroaryl thioetherswere characterized by physical data and spectroscopic techniques.

Reference： [1]Zarnegar, Zohre; Monjezi, Homeyra Rostami; Safari, Javad [Journal of Molecular Structure, 2019, vol. 1193, p. 14 - 23]

78
[ 585-74-0 ]
1-(m-tolyl)ethan-1-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	Stage #1: 3-Methylacetophenone With Ru⁽²⁺⁾2C₂H₃O₂^(1-)C₇₇H₁₀₈O₆P₂; ammonium acetate; hydrogen In 2,2,2-trifluoroethanol at 20℃; for 20h; Heating; Autoclave; Stage #2: With hydrogenchloride In 2,2,2-trifluoroethanol; water at 80℃; for 6h;	4 Example 4 3-methylacetophenone (1 mmol, 134 mg), Ru(OAc) 2L5 (0.5 mol%), NH4OAc in an argon atmosphere(2mmol, 154mg) and trifluoroethanol (2mL) were added to a 5mL ampule,The reaction flask was placed in an autoclave, and the hydrogen was exchanged three times, each time charging 10 atm of hydrogen.The last time I rushed into 50atm,The autoclave is placed in an oil bath which is preheated to a corresponding temperature in advance.Heat 20 stirring for a few hours, cool to room temperature, slowly release hydrogen,Take out the reaction flask and add 3 mL of 6M hydrogen chloride solution.Heat at 80 ° C for 6 hours, cooling,Wash twice with ether and neutralize to pH 10 with 4M sodium hydroxide solution.It was extracted three times with diethyl ether, and the organic phases were combined and dried over anhydrous sodium sulfate.Vacuum drying,Obtaining pure (R)-1-(m-tolyl)ethan-1-amine,120mg, 89%Yield, 91% ee.

Reference： [1]Current Patent Assignee: SHENZHEN CATALYS TECH; SHENZHEN INNOVATION CENTER OF SMALL MOLECULE DRUG DISCOVERY; SHENZHEN CATALYS TECHNOLOGY - CN109851506, 2019, A Location in patent: Paragraph 0071-0073

79
[ 21149-17-7 ]
[ 585-74-0 ]
(Z)-methyl 3-(3-acetyl-5-methylphenyl)-2-(((benzyloxy)carbonyl)amino)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	Stage #1: 3-Methylacetophenone With 2-(2,3-dihydroxypropoxy)-4,5-dimethoxybenzonitrile; toluene-4-sulfonic acid In toluene for 12h; Reflux; Stage #2: methyl 2-(benzyloxycarbonylamino)acrylate With 1,1,1,3',3',3'-hexafluoro-propanol; C₄H₆O₄; silver(I) acetate; palladium diacetate In water at 80℃; for 24h; Stage #3: In water at 80℃; for 1h;

Reference： [1]Xie, Shuguang; Li, Sen; Ma, Wenqian; Xu, Xiaohua; Jin, Zhong [Chemical Communications, 2019, vol. 55, # 82, p. 12408 - 12411]

80
[ 81335-87-7 ]
[ 585-74-0 ]
C₁₇H₁₅N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59%	With tris(triphenylphosphine)ruthenium(II) chloride; potassium hydroxide; In toluene;Reflux;	Sub-1 (35.0g, 255.1mmol), 3'-methylacetophenone (51.4g, 382.7mmol), tris (triphenylphosphine) ruthenium (II) dichloride (2mol%) and Potassium hydroxide (15.7g, 280.7mmol) and toluene (300mL) were added to the reaction flask, heated and stirred to reflux, and water was separated by a reflux reflux condenser. When the reaction is over, drop to room temperature and filter on a pad of silica gel. The product was further purified by column (eluent: n-hexane / ethyl acetate = 2/100), and finally the intermediate Sub-2 (35.1 g, yield 59%) was obtained by crystallization from isopropanol.

Reference： [1]Patent: CN110452271,2019,A .Location in patent: Paragraph 0044-0046

81
[ 20712-12-3 ]
[ 585-74-0 ]
C₁₆H₁₂BrN [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tris(triphenylphosphine)ruthenium(II) chloride; potassium hydroxide; In toluene;Reflux;	The intermediate Sub-1 (40.0g, 198.0mmol),3'-methylacetophenone (39.8g, 297.0mol),Tris (triphenylphosphine) ruthenium (II) dichloride (3mol%), potassium hydroxide (12.2g, 217.8mmol) and toluene (400mL) were added to the reaction flask, heated and stirred to reflux, through the reflux condenser Divide. When the reaction is over, drop to room temperature and filter with silica gel. The product was further purified by column (eluent: n-hexane / ethyl acetate = 2/100), concentrated, and finally crystallized by isopropanol to obtain intermediate Sub-2 (33.6g, yield 57%)

Reference： [1]Patent: CN110872328,2020,A .Location in patent: Paragraph 0053-0055

82
[ 99-98-9 ]
[ 585-74-0 ]
(E)-N,N-dimethyl-4-((1-(m-tolyl)ethylidene)amino)aniline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
48%	With potassium carbonate In dichloromethane; water; toluene at 160℃; Dean-Stark;	General Procedure D: synthesis of ketimines substrates General procedure: An oven-dried round bottom flask equipped with a magnetic stirring bar was added correspondingketone (1.0 equiv) and N,N-Dimethyl-p-phenylenediamine (1.2-1.5 equiv) or N,N-Dimethyl-pphenylenediaminedihydrochloride (basified with aqueous K2CO3 in CH2Cl2 before using) and toluene (0.2M). The mixture were heated at 160 oC overnight under Dean Stark conditions. The reaction wasthen allowed to cool to room temperature and concentrated in vacuo. The residue was recrystallizedfrom ethanol to yield ketimine substrate.

Reference： [1]Wang, Gang-Wei; Wheatley, Matthew; Simonetti, Marco; Cannas, Diego M.; Larrosa, Igor [Chem, 2020, vol. 6, # 6, p. 1459 - 1468]

83
[ 51012-64-7 ]
[ 585-74-0 ]

Yield	Reaction Conditions	Operation in experiment
89%	With diethyl ether In lithium hydroxide monohydrate at 20℃; for 1.5h; Schlenk technique; Irradiation;	3. General procedure for the reaction of reductive dehalogenation General procedure: To a 10 mL schlenk tube, 1 (0.2 mmol), H2O (1.6 mmol) and Et2O (4 mL) were added in sequence. The reaction mixture was stirred and irradiated by 40 W Kessil purple LED (390 nm) at room temperature . After the reaction was completed, the reaction mixture was purified by flash column chromatography using PE/EtOAc as the eluent to give the desired product.
	Multi-step reaction with 2 steps 1: potassium carbonate / propan-2-one / Reflux 2: 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl-4',4',5',5'-tetramethyl-1,3,2-dioxaborolane; sodium tertiary butoxide; 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine cobalt(II)dichloride / tetrahydrofuran; methanol / 3 h / 65 °C / Schlenk technique; Inert atmosphere

Reference： [1]Chen, Jiajia; Chen, Jianhui; Luo, Yanshu; Xia, Yuanzhi; Zhang, Jinrong [Tetrahedron Letters, 2022]
[2]Gao, Kecheng; Xu, Man; Cai, Cheng; Ding, Yanghao; Chen, Jianhui; Liu, Bosheng; Xia, Yuanzhi [Organic Letters, 2020, vol. 22, # 15, p. 6055 - 6060]

84
[ 2786-51-8 ]
[ 585-74-0 ]
[ 1268700-02-2 ]

Yield	Reaction Conditions	Operation in experiment
87%	With tert.-butylhydroperoxide; iodine In water; dimethyl sulfoxide at 60℃; for 3h;	Benzo[d]thiazol-2-arylmethanones 3; General Procedure General procedure: A mixture of benzothiazole 1 (0.4 mmol), aryl ketone 2 (0.4 mmol), I2 (0.4 mmol) and TBHP (70%, 1.2 mmol) was heated at 60 °C in DMSO for 3 h. After completion of the reaction, EtOAc and saturated aqueous Na2S2O3 solution were added. The organic layer was separated, dried (MgSO4), filtered and evaporated under reduced pressure. The crude residue was purified by flash chromatography (silica gel, petroleum ether/ethyl acetate, 25:1 to 8:1) to give product 3a-t.

Reference： [1]Wang, Bin; Zhang, Qianwei; Guo, Zhongqi; Ablajan, Keyume [Synthesis, 2020, vol. 52, # 2, p. 3058 - 3064]

85
[ 2114-02-5 ]
[ 585-74-0 ]
N-(4-(3-methylphenyl)-1,3-thiazol-2-yl)guanidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With Oxone; sodium bromide In methanol at 60℃; for 2h;	14 Example 14: Synthesis of N-(4-(3-methylphenyl)-1,3-thiazol-2-yl)guanidine (Formula 21) Combine 3-methylacetophenone (0.54 g, 4.0 mmol)Dissolved in MeOH (40 mL),Add Oxone (2.70g, 4.4 mmol) sequentiallyAnd NaBr (0.45 g, 4.4 mmol),Add amidinothiourea (0.47 g, 4.0 mmol) toInto the mixture,Slowly increase to 60,The reaction is completed after refluxing for 2h,The reaction mixture is filtered,The filtrate was taken and concentrated in vacuo.Dissolve the crude product in water,Adjust the pH to 8-9 with ammonia water,There is solid precipitation,Suction filtration, take the filter cake, and dry. At last,The crude product obtained was recrystallized with MeOH,N-(4-(3-methylphenyl)-1,3-thiazol-2-yl)guanidine (0.86g) was obtained as the product with the following structure,The yield was 93%.

Reference： [1]Current Patent Assignee: XIHUA UNIVERSITY - CN111825633, 2020, A Location in patent: Paragraph 0014

86
[ 5651-83-2 ]
[ 585-74-0 ]
(E)-3-(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)-1-(m-tolyl)prop-2-en-1-one [ No CAS ]
3-(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)-1,5-di-m-tolylpentane-1,5-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 21% 2: 19%	With potassium hydroxide In methanol; water at 40℃; for 68h; Inert atmosphere;	Generalprocedure for the synthesis of chalcones 7a-b General procedure: To a solution of 3-methylacetophenone (0.720mL, 5.260 mmol) in methanol (15.000 mL) was firstly added 4-O-propargylvanillin (1b) (1.000 g, 5.260 mmol) and then anaqueous solution KOH (50%, 1 mL/mmol of 3-methylacetophenone) or 5.260 mL. Thereaction mixture was stirred at 40 °C for 68 h, under a nitrogen atmosphere.The products, 7a (0.342 g, yield 21%) and 7b (0.308 g, yield 19%), were obtained after separation and purification ofthe residue of the reaction by CC followed by prep. TLC in n-hexane-EtOAc 85:15, using the standard procedure as describedabove (see the synthesis of chalcones6a-d). (E)-3-(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)-1-(m-tolyl)prop-2-en-1-one (7a). Yellow oil,Rf 0.27; n-hexane-EtOAc 17:3 v/v. IR (CHCl3)nmax 3650, 3288, 3008, 2922, 2865, 2121, 1658,1592, 1509, 1465, 1453, 1422, 1376, 1336, 1310, 1260, 1220, 1162, 1142, 1058,1022, 983, 926, 846, 793, 759, 719, 680, 575, 554 cm-1. 1HNMR (400 MHz, CDCl3): δ (ppm) 7.81-7.76 (m, 2H), 7.73 (d, J 15.6 Hz,1H), 7.38 (d, J 15.6 Hz, 1H), 7.36-7.34 (m, 2H), 7.21 (dd, J 8.3,1.9 Hz, 1H), 7.15 (d, J 1.9 Hz, 1H), 7.03 (d, J 8.3 Hz, 1H), 4.79(d, J 2.4 Hz, 2H), 3.91 (s, 3H), 2.54 (t, J 2.4 Hz, 1H), 2.41 (s,3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 190.9, 150.0,149.2, 144.8, 138.7, 138.6, 133.6, 129.3, 129.2, 128.6, 125.4, 122.7, 121.0,114.0, 111.1, 78.3, 76.5, 56.8, 56.2, 21.6. Anal. calcd for C20H18O3:C, 78.41; H, 5.92; O, 15.67. Found: C, 78.43; H, 5.96. 3-(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)-1,5-di-m-tolylpentane-1,5-dione (7b) Pale yellow oil, Rf 0.21, n-hexane-EtOAc 17:3 v/v.IR (CHCl3)nmax 3264, 2922, 2852, 1681, 1600, 1586, 1515,1452, 1422, 1363, 1260, 1143, 1065, 926, 856, 792, 690, 602, 544 cm-1.1H NMR (400 MHz, CDCl3): δ (ppm) 7.76-7.70 (m, 4H), 7.37-7.28 (m, 4H), 6.93 (d, J 8.8 Hz, 1H), 6.82 (d, J6.3 Hz, 2H), 4.68 (d, J 2.3Hz, 2H), 4.02 (p, J 7.0 Hz, 1H), 3.80 (s, 3H), 3.44 (dd, J 16.6, 7.0 Hz, 2H), 3.32 (dd, J16.6, 7.0 Hz, 2H), 2.47(t, J 2.3 Hz,1H), 2.38 (s, 6H). 13C NMR (100 MHz, CDCl3): δ (ppm) 199.1(x2), 149.7, 145.7, 138.6 (x2), 138.3, 137.3 (x2), 134.0 (x2), 128.9 (x2),128.7 (x2), 125.6 (x2), 119.1, 114.7, 112.1, 79.0, 75.9, 57.0, 56.1, 45.3 (x2),37.2, 21.6 (x2). Anal. calcd. for C29H28O4:C, 79.07; H, 6.41; O, 14.53. Found: C, 79.10; H, 6.44.

Reference： [1]Ngameni, Bathélémy; Cedric, Kamdoum; Mbaveng, Armelle T.; Erdoğan, Musa; Simo, Ingrid; Kuete, Victor; Daştan, Arif [Bioorganic and Medicinal Chemistry Letters, 2021, vol. 35]

87
[ 100-51-6 ]
[ 585-74-0 ]
[ 16619-32-2 ]

Yield	Reaction Conditions	Operation in experiment
82%	With oxygen; caesium carbonate In acetonitrile at 20℃; for 24h; chemoselective reaction;
81%	With potassium fluoride; tetrabutyl ammonium fluoride; silver(I) triflimide In water at 60℃; for 12h;	Typical procedure for 7a General procedure: The reaction of acetophenone and benzyl alcohol was set up according to the following procedure: Acetophenone (120 mg), benzyl alcohol (129 mg), AgNTf2 (116 mg), KF (17.4 mg), TBAF (74 mg) and TPT-ZnMS (10 mg) were added to a reaction tube under air atmosphere. Water (3.5 mL) and a stir bar were added in sequence and the mixture was stirred for 12 h at 60 oC condition under air atmosphere.

Reference： [1]Zhu, Guanxin; Duan, Zheng-Chao; Zhu, Haiyan; Qi, Minghui; Wang, Dawei [Molecular catalysis, 2021, vol. 505]
[2]Zhu, Guanxin; Duan, Zheng-Chao; Zhu, Haiyan; Ye, Dongdong; Wang, Dawei [Chinese Chemical Letters, 2022, vol. 33, # 1, p. 266 - 270]

88
[ 585-74-0 ]
[ 446-07-1 ]

Reference： [1]Chemical Communications,2021,vol. 57,p. 4544 - 4547

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	585-74-0	MDL No. :	MFCD00008742
Formula :	C₉H₁₀O	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	FSPSELPMWGWDRY-UHFFFAOYSA-N
M.W :	134.18	Pubchem ID :	11455
Synonyms :		Chemical Name :	1-(m-Tolyl)ethanone

Num. heavy atoms :	10
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.22
Num. rotatable bonds :	1
Num. H-bond acceptors :	1.0
Num. H-bond donors :	0.0
Molar Refractivity :	41.6
TPSA :	17.07 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.59 cm/s

Log Po/w (iLOGP) :	2.04
Log Po/w (XLOGP3) :	2.15
Log Po/w (WLOGP) :	2.2
Log Po/w (MLOGP) :	2.1
Log Po/w (SILICOS-IT) :	2.64
Consensus Log Po/w :	2.22

[ CAS No. 585-74-0 ] {[proInfo.proName]}

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Calculated chemistry of [ 585-74-0 ]

Physicochemical Properties

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[ 585-74-0 ] Synthesis Path-Upstream 1~8

[ 585-74-0 ] Synthesis Path-Downstream 1~88

Related Functional Groups of
[ 585-74-0 ]

Aryls

Ketones

Precautionary Statements-General

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Inquiry

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	2.0
Bioavailability Score :	0.55

Log S (ESOL) :	-2.4
Solubility :	0.529 mg/ml ; 0.00394 mol/l
Class :	Soluble
Log S (Ali) :	-2.14
Solubility :	0.97 mg/ml ; 0.00723 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-3.09
Solubility :	0.11 mg/ml ; 0.000818 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.0

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Yield	Reaction Conditions	Operation in experiment
96%	With Oxone; ammonium bromide In methanol for 0.666667 h; Reflux	General procedure: Oxone (1.352 g, 2.2 mmol) was added to the well stirred solution of substrate (2 mmol) and NH₄Br (0.215 g, 2.2 mmol) in methanol (10 ml) and the reaction mixture was allowed to stir at room temperature (or reflux temperature). After completion of the reaction, as monitored by TLC, the reaction mixture was quenched with aqueous sodium thiosulfate, and extracted with ethyl acetate (3.x.25 ml). Finally, the combined organic layer was washed with water, dried over anhydrous sodium sulfate, filtered and removal of solvent in vacuo yielded a crude residue, which was further purified by column chromatography over silica gel (finer than 200 mesh) to afford pure products. All the products were identified on the basis of ¹H NMR and mass spectral data.
80%	With bromine In 1,4-dioxane; diethyl ether at 20℃; for 5 h;	To a solution of 1-m-tolyl-ethanone (6.Og, 44.72mmol) in dioxane (5ml), bromine (7.14g, 44.72mmol) in dioxane (10ml) and ether (15ml) was added and stirred at room temperature for 5 hr. The reaction mixture was poured into ice water and the compound was extracted using ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, filtered and then evaporated to give crude 2- bromo- 1-m-tolyl-ethanone, 7.6g (80percent). The crude compound obtained was used in the next step without further purification.

Yield	Reaction Conditions	Operation in experiment
84%	at 80℃; for 2 h;	Sodium hydride (3.1g, 77.1mmol) and diethylcarbonate were added to 3- methyl acetophenone (4.5g, 33.54mmol). The reaction mixture was stirred for 2hrs with heating at 80°C. Once the reaction was completed, ice water and acetic acid were added thereto. The resulting mixture was washed with saturated saline and extracted with ethyl acetate. The organic layer was separated, dried over anhydrous MgS04 and concentrated under a reduced pressure. The resulting residue was purified by flash chromatography to obtain 5.8g of the titled compound (yield: 84 percent). @H-NMR (200MHz, CDC13) 8 7.83-7.63 (m, 2H) 7.42-7.28 (m, 2H) 4.27~4.18 (m, 2H) 3.97 (s, 2H) 2.40 (s, 3H) 1.36~1.23 (m, 3H)
84%	at 80℃; for 2 h;	Sodium hydride (3.1 g, 77.1 mmol) and diethyl carbonate were combined with 3-methylacetophenone (4.5 g, 33.54 mmol). The mixture was stirred for 2 hours at 80°C. After the reaction was completed, ice water and acetic acid were added thereto. Then, the mixture was extracted with ethyl acetate/saturated sodium chloride. The extract was dried over anhydrous magnesium sulfate, concentrated, and the resulting residue was purified by column chromatography to obtain 3-oxo-3-m-tolylpropionate ethyl ester (5.8 g, yield 84 percent). ¹H NMR (200MHz, CDCl3) : No. 7.83-7.63 (m, 2H), 7.42-7.28 (m, 2H), 4.27-4.18 (m, 2H), 3.97 (s, 2H), 2.40 (s, 3H), 1.36-1.23 (m, 3H).
46.9%	Stage #1: With sodium hydride In toluene for 0.5 h; Heating / reflux Stage #2: With acetic acid In toluene at 20℃;	Example 10; Ethyl 3-methyl-benzoyl-acetate (1 -10-a); To a vigorously stirred suspension of NaH (564 mg, 48.5 mmol) and CO(OEt)₂ (5.73 g, 48.5 mmol) in anhydrous toluene (50ml) was added dropwise a solution of 3-methylacetophenone (4.33 g, 32.3 mmole) in toluene under reflux. The mixture was allowed to reflux and was stirred for 30 min after the addition was complete. When cooled to room temperature, the mixture was acidified with glacial AcOH. After ice-cold water was added, the mixture was extracted with toluene. The organic layer was dried over MgSO₄, and evaporated. The residue was further chromatographed over silica gel by elution with CH₂CI₂-/i-haxane (3:2) to afford l-10-b as light-yellow liquid (3.13g, 46.9percent) <n="35"/>¹H-NMR (DMSO-t/6, 200 MHz): δ 7.68-7.72 (2H, m, H-4, H-6) , 7.32-7.36 (2H, m, H-2, H-3) , 4.16 (2H, q, J = 7, CH₂CH₃) , 3.94 (2H, s, H-10) , 2.38 (3H, s, CH₃), 1.2 (3H, t, J = 7,CH₂CHa) MS (m/z) 206 (El+) Anal, calcd for C12H14O3: C, 69.88; H, 6.84; Found: C, 69.72; H, 6.95.

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