Name: 1121-66-0|Cyclohept-2-enone|90%
Brand: Ambeed
SKU: A190323
Price: 8.0 USD
Availability: InStock
Rating: 96 (35 reviews)

1
[ 1121-66-0 ]
[ 502-42-1 ]

Yield	Reaction Conditions	Operation in experiment
95%	With hydrogen In acetone for 8h;
94%	With hydrogen In ethanol at 20℃; for 1h; chemoselective reaction;
	With hydrogen; palladium

99 % Chromat.	With dicobalt octacarbonyl; water In 1,2-dimethoxyethane for 2h; Heating;
99 % Chromat.	With isopropyl alcohol In benzene for 1h; Heating;
	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; sodium formate; N-tosylethylenediamine In water at 60℃; for 5h; Inert atmosphere; chemoselective reaction;
99 %Chromat.	With (1,4-dimethyl-5,7-diphenyl-1,2,3,4-tetrahydro-6H-cyclopenta[b]pyrazin-6-one)(triphenylphosphine)(dicarbonyl)iron; caesium carbonate; isopropyl alcohol at 90℃; for 16h;
91 %Chromat.	With methanol; C₂₅H₂₉ClNO₂Rh; potassium carbonate at 90℃; for 1h; chemoselective reaction;	2.2. Transfer hydrogenation of unsaturated ketones in methanol A Radley tube was charged with an unsaturated ketone (0.3mmol), catalyst (0.003 mmol) and K2CO3 (0.25 eq), to which was introduced MeOH (1.5 mL). The reaction mixture was heated to reflux at 90 °C for 1 h. The resulting mixture was then cooled to room temperature, followed by solvent evaporation under vacuum. The product was purified by flash column chromatography (hexane/ethyl acetate, 4:1).
92 %Chromat.	With hydrogen In water at 80℃; for 20h; Autoclave;

Reference： [1]Ali, Hussein M.; Naiini, Ahmad A.; Brubaker, Carl H. [Tetrahedron Letters, 1991, vol. 32, # 40, p. 5489 - 5492]
[2]Kantam, Mannepalli Lakshmi; Kishore, Ramineni; Yadav, Jagjit; Sudhakar, Medak; Venugopal, Akula [Advanced Synthesis and Catalysis, 2012, vol. 354, # 4, p. 663 - 669]
[3]Koetz; Rosenbusch [Chemische Berichte, 1911, vol. 44, p. 464][Justus Liebigs Annalen der Chemie, 1913, vol. 400, p. 74] Koetz; Blendermann; Maehnert; Rosenbusch [Justus Liebigs Annalen der Chemie, 1913, vol. 400, p. 83]
[4]Lee, Hee-Yoon; An, Mihyun [Tetrahedron Letters, 2003, vol. 44, # 14, p. 2775 - 2778]
[5]Doi, Takashi; Fukuyama, Takahide; Horiguchi, Jiro; Okamura, Takahiro; Ryu, Ilhyong [Synlett, 2006, # 5, p. 721 - 724]
[6]Location in patent: experimental part Li, Xuefeng; Li, Liangchun; Tang, Yuanfu; Zhong, Ling; Cun, Linfeng; Zhu, Jin; Liao, Jian; Deng, Jingen [Journal of Organic Chemistry, 2010, vol. 75, # 9, p. 2981 - 2988]
[7]Lator, Alexis; Gaillard, Sylvain; Poater, Albert; Renaud, Jean-Luc [Chemistry - A European Journal, 2018, vol. 24, # 22, p. 5770 - 5774]
[8]Aboo, Ahmed H.; Begum, Robina; Zhao, Liangliang; Farooqi, Zahoor H.; Xiao, Jianliang [Cuihua Xuebao/Chinese Journal of Catalysis, 2019, vol. 40, # 11, p. 1795 - 1799]
[9]Klarner, Mara; Bieger, Sandra; Drechsler, Markus; Kempe, Rhett [Zeitschrift fur Anorganische und Allgemeine Chemie, 2021, vol. 647, # 22, p. 2157 - 2161]

2
[ 4096-38-2 ]
[ 1121-66-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With peracetic acid In tetrachloromethane; dichloromethane at 0℃; for 0.3h;
80%	With 2,2,6,6-tetramethyl-piperidine-N-oxyl; iron(III) chloride In water; ethyl acetate at 20℃; for 2h;
	With aluminum isopropoxide; p-benzoquinone; benzene

	With manganese(IV) oxide In Petroleum ether
	(oxidation);
	With chromic acid
	Jones oxidation;
12 %Chromat.	With [(η⁵-C₅Me₅)Ir(6,6'-dihydroxy-2,2'-bipyridine)(H₂O)]OTf₂ In water; <i>tert</i>-butyl alcohol at 40℃; for 24h;

Reference： [1]Corey, E. J.; Barrette, Ernie-Paul; Magriotis, Plato A. [Tetrahedron Letters, 1985, vol. 26, # 48, p. 5855 - 5858]
[2]Kumar, R. Senthil; Karthikeyan; Perumal, Paramasivan T. [Canadian Journal of Chemistry, 2008, vol. 86, # 7, p. 720 - 725]
[3]Mousseron et al. [Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1956, vol. 243, p. 1880] Jacquier; Fraisse [Bulletin de la Societe Chimique de France, 1956, p. 559] Hodgkins; Flores [Journal of Organic Chemistry, 1963, vol. 28, p. 3356,3358]
[4]Ansell,M.F. et al. [Journal of the Chemical Society C: Organic, 1968, p. 217 - 225]
[5]Olah,G.A.; Liang,G. [Journal of the American Chemical Society, 1972, vol. 94, # 18, p. 6434 - 6441]
[6]Heap,N.; Whitham,G.H. [Journal of the Chemical Society B: Physical Organic, 1966, p. 164 - 170]
[7]Kaneda, Kiyotomi; Jitsukawa, Koichiro; Itoh, Takashi; Teranishi, Shiichiro [Journal of Organic Chemistry, 1980, vol. 45, p. 3004 - 3009]
[8]Ngo, Anh H.; Adams, Michael J.; Do, Loi H. [Organometallics, 2014, vol. 33, # 23, p. 6742 - 6745]

3
[ 502-42-1 ]
[ 1121-66-0 ]

Yield	Reaction Conditions	Operation in experiment
88%	With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In fluorobenzene; dimethyl sulfoxide at 65℃; for 6h;
	With lithium hydroxide monohydrate; calcium carbonate at 28℃; durch Einleiten von Bromdampf und Behandeln des Reaktionsprodukts mit Anilin;
	(i) LDA, THF, (ii) (PhSe)2, Br₂, (iii) O₃; Multistep reaction;

	Multi-step reaction with 2 steps 1: 1.) Br₂, 2.) 36.5percent aq. HCl / 1.) Ethanol, room temp., 0.5 h, 2.) ethanol, reflux, 0.5 h 2: 100 percent Chromat_. / O₃, HNEt₂ / CH₂Cl₂ / 1.) - 78 deg C, 2.) addition to refluxing carbon tetrachloride
	Multi-step reaction with 2 steps 1: 81 percent / diethyl ether / 0.25 h / 0 - 20 °C 2: 74 percent / NaHCO₃ / H₂O; CH₂Cl₂
	Multi-step reaction with 2 steps 1: sodium iodide; triethylamine / acetonitrile / 16 h / 20 °C / Inert atmosphere 2: palladium diacetate; p-benzoquinone / acetonitrile / 3 h / 20 °C / Inert atmosphere
	Stage #1: Cycloheptanon With toluene-4-sulfonic acid In dichloromethane at 20℃; for 0.166667h; Stage #2: With NBS In dichloromethane at 20℃; for 16h; Cooling with ice; Stage #3: With lithium carbonate; lithium bromide In N,N-dimethyl-formamide at 130℃; for 3h; Inert atmosphere;	1 Synthesis of 2-cyclohepten-1-one (3) Cycloheptanone (5.608 g, 50.00 mmol) was added to a 500 mL single-neck flask, and anhydrous DCM (50 mL) was added. P-toluenesulfonic acid monohydrate (85.0 mg, 0.50 mmol) was slowly added, and the reaction was carried out at room temperature for 10 min. Under ice-cooling, NBS (9.788 g, 55.00 mmol) was slowly added, the temperature was gradually raised to room temperature, and the reaction was carried out at room temperature for 16 h to stop the reaction. Under ice-cooling, saturated sodium thiosulfate solution (40 mL) was added, and the solution was separated. The aqueous phase was extracted with DCM (3 x 100 mL) and the organic phases were combined. The organic phase was dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. Finally, it was purified by silica gel column chromatography (petroleum ether:ethyl acetate 10:1) to obtain the crude bromocycloheptanone.Under argon protection, lithium carbonate (0.870g, 11.77mmol) and lithium bromide (1.022g, 11.77mmol) were added to a 200mL Shrek bottle, followed by anhydrous DMF (50mL) and bromocycloheptanone (1.500g, 7.85g) mmol), heated to 130 °C, and continued to stir the reaction for 3 h to stop the reaction. The temperature of the reaction solution was lowered to room temperature, water (10 mL) was added to quench the reaction, and the layers were separated. The aqueous phase was extracted with Et2O (3 x 100 mL) and the organic phases were combined. The organic phase was dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. Finally, it was purified by silica gel column chromatography (petroleum ether:diethyl ether 30:1) to give cycloheptenone 3 (0.600 g, 70% yield for two steps) as a colorless oil.

Reference： [1]Nicolaou; Montagnon; Baran; Zhong [Journal of the American Chemical Society, 2002, vol. 124, # 10, p. 2245 - 2258]
[2]Koetz; Blendermann; Karpati; Rosenbusch [Justus Liebigs Annalen der Chemie, 1913, vol. 400, p. 53] Koetz; Blendermann; Maehnert; Rosenbusch [Justus Liebigs Annalen der Chemie, 1913, vol. 400, p. 83]
[3]Reich,H.J. et al. [Journal of the American Chemical Society, 1975, vol. 97, # 19, p. 5434 - 5447]
[4]Toshimitsu, Akio; Owada, Hiroto; Uemura, Sakae; Okano, Masaya [Tetrahedron Letters, 1982, vol. 23, # 20, p. 2105 - 2108]
[5]Engman, Lars [Tetrahedron Letters, 1985, vol. 26, # 51, p. 6385 - 6388]
[6]Liu, Xufang; Zhang, Wei; Wang, Yujie; Zhang, Ze-Xin; Jiao, Lei; Liu, Qiang [Journal of the American Chemical Society, 2018, vol. 140, # 22, p. 6873 - 6882]
[7]Current Patent Assignee: CHINA AGRICULTURAL UNIVERSITY - CN113773180, 2021, A Location in patent: Paragraph 0008; 0021-0024

4
[ 1121-66-0 ]
[ 4096-38-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium tetrahydroborate; cerium(III) chloride In methanol at 25℃; for 0.0833333h;
97%	With sodium tetrahydroborate; cerium(III) chloride heptahydrate In methanol at 0 - 20℃; for 3h; Inert atmosphere; Schlenk technique;
73%	With sodium tetrahydroborate; cerium(III) chloride In methanol at 0℃;

	With potassium tri-sec-butyl-borohydride
	With sodium tetrahydroborate; CeCl*7H₂O In methanol for 0.166667h;
	With sodium tetrahydroborate; cerium(III) chloride heptahydrate In methanol at 0℃; for 0.5h;
	With methanol; sodium tetrahydroborate; cerium(III) chloride heptahydrate at 20℃; for 2.5h;	12B.A To a solution of cyclohept-2-enone (10 g, 91 mmol) and cerium(III) chloride heptahydrate (33.8 g, 91 mmol) in methanol (45.5 mL) was added sodium borohydride (3.43 g, 91 mmol) portion- wise over 10 minutes period with cooling in a water bath. The reaction mixture was then stirred for 2.5 hr at room temperature. The reaction was quenched by addition of water (45 mL) and then was extracted with pentane (4 x 100 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under- 96 -ATI-2514175vl reduced pressure to afford the title compound (8.30 g, 74.0 mmol, 82 % yield) as an oil that was used without further purification. 1H NMR (400 MHz, DMSO-d6) δ ppm 5.49 - 5.71 (m, 2 H), 4.66 (d, J=4.29 Hz, 1 H), 4.05 - 4.20 (m, 1 H), 1.07 - 2.14 (m, 8 H).
	With diisobutylaluminium hydride In hexane; dichloromethane at -78℃; for 1.5h;	24.1 Step 1 : Dibal-H (13.0 ml, 1.0M in hexanes) was added drop wise to a cooled (-78 °C) solution of cyclohept-2-en-l-one (1.0 g, 9.1 mmol) in DCM (36.3 ml). The mixture was stirred for 1.5 hours. Methanol (2.5 mL) was added and the reaction was allowed to warm to room temperature. Saturated aqueous sodium potassium tartrate (100 ml) and ethyl acetate (100 ml) were added and the mixture was vigorously stirred until the emulsion broke (overnight). The layers were then separated and the aqueous layer was extracted with dichloromethane (3x). The combined organics were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (0 to 50% ethyl acetate/hexanes) to afford cyclohept-2-en-l-ol as a colorless oil.
	With methanol; sodium tetrahydroborate at 0 - 40℃; Inert atmosphere;
	With methanol; sodium tetrahydroborate; cerium(III) chloride Inert atmosphere;

Reference： [1]Huber, Robert S.; Jones, Graham B. [Journal of Organic Chemistry, 1992, vol. 57, # 21, p. 5778 - 5780]
[2]Rideau, Emeline; You, Hengzhi; Sidera, Mireia; Claridge, Timothy D. W.; Fletcher, Stephen P. [Journal of the American Chemical Society, 2017, vol. 139, # 15, p. 5614 - 5624]
[3]Marr, Felix; Froehlich, Roland; Wibbeling, Birgit; Diedrich, Christian; Hoppe, Dieter [European Journal of Organic Chemistry, 2002, # 17, p. 2970 - 2988]
[4]Fortunato,J.M.; Canem,B. [Journal of Organic Chemistry, 1976, vol. 41, # 12, p. 2194 - 2200]
[5]Trost, Barry M.; Richardson, Jeffery; Yong, Kelvin [Journal of the American Chemical Society, 2006, vol. 128, # 8, p. 2540 - 2541]
[6]Trost, Barry M.; Xu, Jiayi; Schmidt, Thomas [Journal of the American Chemical Society, 2008, vol. 130, # 36, p. 11852 - 11853]
[7]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2012/145569, 2012, A1 Location in patent: Page/Page column 96; 97
[8]Current Patent Assignee: MERCK & CO INC - WO2014/48065, 2014, A1 Location in patent: Page/Page column 90
[9]Zhang, Hua; Zhang, Guo-Min; He, Shuai; Shi, Zhi-Chuan; Zhang, Xiao-Mei; Wang, Ji-Yu [Organic Letters, 2020, vol. 22, # 21, p. 8337 - 8344]
[10]Hirano, Koji; Miura, Masahiro; Xu, Shibo [Organic Letters, 2020, vol. 22, # 22, p. 9059 - 9064]

5
[ 67-56-1 ]
[ 18202-04-5 ]
[ 4630-82-4 ]
[ 1121-66-0 ]
[ 155200-44-5 ]
[ 502-42-1 ]

Reference： [1]Journal of Organic Chemistry,1980,vol. 45,p. 5278 - 5283

6
[ 6283-71-2 ]
[ 1121-66-0 ]
Methyl-8-cyan-2,10-dioxobicyclo<5.3.0>decan-8-carboxylat [ No CAS ]
[ 84763-57-5 ]

Reference： [1]Liebigs Annalen der Chemie,1983,p. 112 - 136

7
[ 6283-71-2 ]
[ 1121-66-0 ]
[ 84763-57-5 ]

Reference： [1]Liebigs Annalen der Chemie,1983,p. 112 - 136

8
[ 33604-67-0 ]
[ 1121-66-0 ]
[ 613-33-2 ]
[ 644-08-6 ]
[ 108011-64-9 ]

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,1989,vol. 46,p. 121 - 130

9
[ 628-92-2 ]
[ 1121-66-0 ]
[ 286-45-3 ]

Yield	Reaction Conditions	Operation in experiment
1: 9% 2: 73%	With Carbon tetrachloride; 18-crown-6 ether In acetonitrile at 10℃;
	With oxygen In neat (no solvent) at 150℃; for 24h;
	With oxygen In acetonitrile at 120℃; for 13h;	2.3.1. Catalytic experiments Briefly, the required amount of UiO-66(Zr Ti)-X (X: NH2, H and NO2) employed as catalyst (0.016mmol of total metal Zr+Ti) was introduced into a reactor vessel (5mL). Subsequently, the olefin reagent (2mmol) dissolved in CH3CN (2.5mL) was added to the vessel. The system was pressurized with O2 at the required value at room temperature (i.e. 5 or 2atm). The reactions were carried out under 600rpm magnetic stirring to ensure that the process is under kinetic control. Catalyst reusability was studied for the most active sample (UiO-66(Zr5.4Ti0.6)-NO2). At the end of the reaction, the solid catalyst was recovered by filtration (Nylon membrane, 0.2μm) and, transferred to a round-bottom flask (50mL) and washed under magnetic stirring with ethanol (20mL) at 80°C for 2h. This procedure was repeated three times. The washed, used solid catalyst was recovered by filtration (Nylon membrane, 0.2μm) and dried in an oven at 100°C for 24h. Before the new catalytic cycle, the solid catalyst was activated at 150°C under vacuum for 16h. Selective radical quenching experiments were carried out following the general reaction procedure described above, but with the addition of radical quenchers (20mol% with respect to the substrate). In particular, dimethylsulfoxide (DMSO) [53-56] or p-benzoquinone [53,54,56,57] were added as selective hydroxyl or superoxide/hydroperoxyl radical scavengers, respectively.

1: 19 %Chromat. 2: 17 %Chromat.

With CH₄N₂*H⁽¹⁺⁾*Pb⁽²⁺⁾*3Br^(1-); oxygen In acetonitrile at 25℃; for 24h; Irradiation;

Reference： [1]Yamamoto, Hiroshi; Mashino, Tadahiko; Nagano, Tetsuo; Hirobe, Masaaki [Journal of the American Chemical Society, 1986, vol. 108, p. 539 - 541]
[2]Blandez, Juan F.; Navalón, Sergio; Álvaro, Mercedes; García, Hermenegildo [ChemCatChem, 2018, vol. 10, # 1, p. 198 - 205]
[3]Santiago-Portillo, Andrea; Navalón, Sergio; Álvaro, Mercedes; García, Hermenegildo [Journal of Catalysis, 2018, vol. 365, p. 450 - 463]
[4]Chiara, Rossella; Corti, Marco; Malavasi, Lorenzo; Mannucci, Barbara; Quadrelli, Paolo; Romani, Lidia [Photochemical and Photobiological Sciences, 2022, vol. 21, # 5, p. 613 - 624]

10
[ 1121-66-0 ]
[ 106-99-0 ]
[ 74063-33-5 ]

Yield	Reaction Conditions	Operation in experiment
47%	Stage #1: 2-Cyclohepten-1-one With aluminum (III) chloride In toluene at 20℃; for 0.666667h; Inert atmosphere; Glovebox; Stage #2: buta-1,3-diene In toluene at 20℃; for 22h; Inert atmosphere; Glovebox;	Bicyclo[5.4.0]undec-9-en-2-one (9) A sample of 1.63 g (12.2 mmol) of AlCl3 was weighed into a thick-walled flask under argon in a glovebag. A solution of 2-cycloheptenone (1.5 mL, 0.988 g/mL, 13.6 mmol) in anhydrous toluene (7.6 mL) was transferred to the flask via syringe. After complexation between the ketone and Lewis acid had proceeded for 40 min at rt, a solution of 1,3-butadiene in toluene (27.4 mL, 20 wt%, 0.806 g/mL, 81.7 mmol) was added via syringe through a septum, which was then replaced with Teflon screw cap. After stirring the reaction at rt for 22 h, the reaction mixture was extracted with ether, and the organic layer was washed twice with water and once with brine. Elution of the ketone from a silica column with 98:2 pentane:ether afforded 1.04 g (6.4 mmol, 47%) of pure ketone 9.
46%	With hydroquinone In dichloromethane for 51h; Ambient temperature;

Reference： [1]Leber, Phyllis A.; Nocket, Anthony J.; Hancock-Cerutti, William; Bemis, Christopher Y.; Khine, Wint Khant; Mohrbacher III, Joseph A.; Baldwin, John E. [Molecules, 2014, vol. 19, # 2, p. 1527 - 1543]
[2]Dauben, William G.; Olsen, Eric G. [Journal of Organic Chemistry, 1980, vol. 45, # 17, p. 3377 - 3382]

11
[ 1121-66-0 ]
[ 100-51-6 ]
[ 71691-93-5 ]

Yield	Reaction Conditions	Operation in experiment
90%	With dmap; lithium perchlorate at -20℃; for 85h;
64%	With indium(III) triflate In acetonitrile at 20℃; for 24h;
62%	With sodium phenyl-methanolate for 12h; Ambient temperature;

62%	With chromium(III) chloride hexahydrate In acetonitrile at 20℃; for 24h;
50%	With bismuth(III) chloride at 20℃; for 24h;	General procedure for the hydroalkoxylation of cyclic enones General procedure: Cyclic enones (1s-t, 1.0 mmol, 1.0 equiv.), alcohol 3 (6 equiv.), and BiCl3 (0.0631 g, 0.20mmol, 20 mol%) were stirred in CH3CN (1 mL) at room temperature for 24 h. Upon completion of the reaction (as indicated by TLC), the reaction mixture was directly concentrated in vacuo. The crude residue obtained was purified by silica gel column chromatography using ethyl acetate and petroleum ether as eluant to afford the pure β-alkoxyl ketone 4m-q.

Reference： [1]Hayashi, Yujiro; Nishimura, Koichi [Chemistry Letters, 2002, # 3, p. 296 - 297]
[2]Yun, Jin-Jin; Zhi, Man-Ling; Shi, Wen-Xiao; Chu, Xue-Qiang; Shen, Zhi-Liang; Loh, Teck-Peng [Advanced Synthesis and Catalysis, 2018, vol. 360, # 14, p. 2632 - 2637]
[3]Hammon,D.P.; Trenerry,V.C. [Journal of the American Chemical Society, 1981, vol. 103, p. 4962]
[4]Yun, Jin-Jin; Liu, Xuan-Yu; Deng, Wei; Chu, Xue-Qiang; Shen, Zhi-Liang; Loh, Teck-Peng [Journal of Organic Chemistry, 2018, vol. 83, # 18, p. 10898 - 10907]
[5]Wu, Zhen; Feng, Xue-Xin; Wang, Qing-Dong; Yun, Jin-Jin; Rao, Weidong; Yang, Jin-Ming; Shen, Zhi-Liang [Chinese Chemical Letters, 2020, vol. 31, # 5, p. 1297 - 1300]

12
[ 1121-66-0 ]
[ 5044-52-0 ]
[ 54598-59-3 ]
[ 54598-60-6 ]

Reference： [1]Liebigs Annales,1995,p. 1061 - 1118

13
[ 64-17-5 ]
[ 1121-66-0 ]
[ 6925-19-5 ]

Yield	Reaction Conditions	Operation in experiment
91%	With bismuth(III) chloride at 20℃; for 24h;	General procedure for the hydroalkoxylation of cyclic enones General procedure: Cyclic enones (1s-t, 1.0 mmol, 1.0 equiv.), alcohol 3 (6 equiv.), and BiCl3 (0.0631 g, 0.20mmol, 20 mol%) were stirred in CH3CN (1 mL) at room temperature for 24 h. Upon completion of the reaction (as indicated by TLC), the reaction mixture was directly concentrated in vacuo. The crude residue obtained was purified by silica gel column chromatography using ethyl acetate and petroleum ether as eluant to afford the pure β-alkoxyl ketone 4m-q.
78%	With indium(III) triflate at 20℃; for 24h;
68%	With chromium(III) chloride hexahydrate In acetonitrile at 20℃; for 24h;

Irradiation;

Reference： [1]Wu, Zhen; Feng, Xue-Xin; Wang, Qing-Dong; Yun, Jin-Jin; Rao, Weidong; Yang, Jin-Ming; Shen, Zhi-Liang [Chinese Chemical Letters, 2020, vol. 31, # 5, p. 1297 - 1300]
[2]Yun, Jin-Jin; Zhi, Man-Ling; Shi, Wen-Xiao; Chu, Xue-Qiang; Shen, Zhi-Liang; Loh, Teck-Peng [Advanced Synthesis and Catalysis, 2018, vol. 360, # 14, p. 2632 - 2637]
[3]Yun, Jin-Jin; Liu, Xuan-Yu; Deng, Wei; Chu, Xue-Qiang; Shen, Zhi-Liang; Loh, Teck-Peng [Journal of Organic Chemistry, 2018, vol. 83, # 18, p. 10898 - 10907]
[4]Noyori,R.; Kato,M. [Bulletin of the Chemical Society of Japan, 1974, vol. 47, p. 1460 - 1466]

14
[ 1121-66-0 ]
[ 201935-46-8 ]

Yield	Reaction Conditions	Operation in experiment
81%	With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane for 1.5h; Heating;
78%	With N-Bromosuccinimide; dibenzoyl peroxide In acetonitrile at 70℃; for 3h;	3 Production of 4-bromocyclohept-2-enone (B) (45 mg, 0.13 mmol) and N-bromosuccinimide (3.32 g, 18.68 mmol) were added to cyclohept-2-enone (A) (1.47 g, 13.34 mmol) After adding acetonitrile (13 ml), the mixture was stirred at 70 ° C for 3 hours. Thereafter, 4-bromocyclohept-2-enone (B) (yield: 78%) was obtained by column chromatography.
78%	With N-Bromosuccinimide; dibenzoyl peroxide In acetonitrile at 70℃; for 3h;	3 production of 4-bromocyclohept-2-enone(B) According to the above reaction scheme, cyclohept-2-enone (A) (1.47 g, 13.34 mmol) Benzoyl peroxide (45 mg, 0.13 mmol) and N-Bromosuccinimide (3.32 g, 18.68 mmol) was added to a solution ofAfter adding acetonitrile (13 ml), the mixture was stirred at 70 ° C for 3 hours. Thereafter, 4-bromocyclohept-2-enone (B) was obtained by column chromatography (Yield: 78%).

	With N-Bromosuccinimide; Perbenzoic acid In tetrachloromethane
	With N-Bromosuccinimide In tetrachloromethane Inert atmosphere;	1 Example 1 Synthesis of 11-cis-7-ring retinals was performed as described previously with some modifications (Fujimoto et al., Chirality 14:340-46 (2002); Akito et al., J. Am. Chem. 102:6370-72 (1980); Caldwell et al., J. Org. Chem. 58:3533-37 (1993). All of the reactions were performed in a dried nitrogen atmosphere unless otherwise specified. 2-Cycloheptenone was first converted into allyl acetate by N-bromosuccinimide bromination in CCl4 followed by treatment with KOAc in hexamethylphosphoramide. Purified 4-acetoxy-2-cycloheptenone (46% from 2-cycloheptenone) was subjected to a Horner-Emmons reaction with diethyl (2-cyanoethyl)phosphonate, which gave an isomeric mixture of two trans/cis (E/Z) cyanoacetates in a 2:1 ratio. The mixture was hydrolyzed with K2CO3 in MeOH:H2O (5:1), and then the hydroxy group of the resulting allylic alcohol was protected with tert-butyldimethylsilyl chloride in pyridine (80% from cycloheptenonyl acetate). The resulting cyano compound was reduced with diisobutylaluminium hydride in CH2Cl2 to an aldehyde and purified by flash chromatography on a silica gel (63%). β-Cyclocitral was reduced with. NaBH4 to β-cyclogeraniol and then reacted with triphenylphosphine hydrobromide in MeOH over 3 days to afford β-cyclogeranyltriphenylphosphonium bromide after the removal of solvent and drying of the residue in vacuum. Wittig reaction of the silylated aldehyde with an excess of phosphonium salt in the presence of potassium tert-butoxide and a catalytic amount of 18-crown-6 in methylene chloride at ambient temperature afforded protected cyclic alcohol in 75% yield. The tert-butyldimethylsilyl protecting group was removed by treatment with tetrabutylammonium fluoride in dry THF, and the resulting alcohol was oxidized with MnO2 in CH2Cl2 to a mixture of two (E/Z) cyclic ketones (2:1 ratio) in 96% yield. This mixture was condensed with triethyl phosphonoacetate under Homer-Emmons conditions, followed by lithium aluminum hydride reduction of the resulting isomeric mixture of ethyl 7-ring retinoates and oxidation of retinols with MnO2 (86%) in CH2Cl2.
	With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane for 3h; Inert atmosphere; Reflux;
	With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane for 3h; Inert atmosphere; Reflux;	4-Acetoxy-2-cycloheptenone (2c). Following the procedure described by Nakanishi:3 to asolution of 2-cyclohepten-1-one (80%, 275 mg, 2 mmol, 1 equiv) in carbon tetrachloride(4 mL) N-bromosuccinimide (500 mg, 2.8 mmol, 2.8 equiv) and benzoyl peroxide (1 mg)were added. After 3 h heating at reflux, the resulting dark brown solution was cooled toroom temperature and petroleum ether (10 mL) was added to precipitate the succinimide, whichwas removed by filtration with additional washing with petroleum ether (5 mL). The filtrate wasconcentrated under reduced pressure to give a solution of crude 4-bromo-2-cycloheptenone in CCl4with a final volume of ca. 1 mL.

Reference： [1]Hudson, Andrew; Della Bona, Maria Antonietta; Waterman, Daniel; Alberti, Angelo; Benaglia, Massimo; Macciantelli, Dante [Journal of the Chemical Society. Perkin Transactions 2 (2001), 1997, # 12, p. 2487 - 2490]
[2]Current Patent Assignee: CHO DANG PHARM - KR101621742, 2016, B1 Location in patent: Paragraph 0058-0060
[3]Current Patent Assignee: CHO DANG PHARM - KR101621739, 2016, B1 Location in patent: Paragraph 0067-0069
[4]Tan; Lou; Borhan; Karnaukhova; Berova; Nakanishi [Angewandte Chemie - International Edition in English, 1997, vol. 36, # 19, p. 2089 - 2093]
[5]Current Patent Assignee: UNIVERSITY OF WASHINGTON; UNIVERSITY OF MINNESOTA SYSTEM - US2016/45453, 2016, A1 Location in patent: Paragraph 0064
[6]Liu, Yang; Mao, Zhongyi; Pradal, Alexandre; Huang, Pei-Qiang; Oble, Julie; Poli, Giovanni [Organic Letters, 2018, vol. 20, # 13, p. 4057 - 4061]
[7]Liu, Yang; Oble, Julie; Poli, Giovanni [Beilstein Journal of Organic Chemistry, 2019, vol. 15, p. 1107 - 1115]

15
[ 646-06-0 ]
[ 1121-66-0 ]
3-oxocycloheptancarboxyaldehyde ethylenacetal [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With (Bu₄N)₂S₂O₈ at 25℃; for 44h; Inert atmosphere; regioselective reaction;	Typical experimental procedure: Dimethyl maleate (72.1 mg, 0.50 mmol) and TBAP (677.0 mg, 1.0 mmol) were added to dry 1,3-dioxolane (5 mL), and the reaction mixture was stirred at 25 °C for 1.5 h under Ar. The reaction mixture was concentrated to give a viscous oil which was diluted with H2O (5 mL), then extracted with CH2Cl2 (10 mL × 3). The combined organic layers were dried over anhyd MgSO4, filtered and concentrated to give an oily residue which was flash chromatographed (SiO2, Et2O/hexane = 1:3) to afford pure dimethyl 2-(1,3-dioxolan-2-yl)butanedioate (106.9 mg, 98%).
55%	With benzophenone for 5h; Irradiation;
	With (Bu₄N)₂S₂O₈ at 25℃; Yield given;

Reference： [1]Location in patent: experimental part Jung, Jae Chul; Kim, Yong Hae; Lee, Kieseung [Tetrahedron Letters, 2011, vol. 52, # 36, p. 4662 - 4664]
[2]Manfrotto, Cristina; Mella, Mariella; Freccero, Mauro; Fagnoni, Maurizio; Albini, Angelo [Journal of Organic Chemistry, 1999, vol. 64, # 14, p. 5024 - 5028]
[3]Kim, Yong Hae; Choi, Hyun Chul [Phosphorus, Sulfur and Silicon and the Related Elements, 1997, vol. 120-121, p. 327 - 328]

16
[ 1121-66-0 ]
[ 557-20-0 ]
(S)-3-ethylcycloheptan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With copper(I) trifluoromethanesulfonate benzene; bis[(S,S)-H₈-BINOL][(R)-BINOL]diphosphite In diethyl ether at -30℃; for 3h;
99%	With 1-[2-((S)-1-hydroxy-3,3-dimethyl-2-butanylamino)-2-oxoethyl]-3-benzylbenzimidazolium chloride; copper(II) bis(trifluoromethanesulfonate) In tetrahydrofuran; hexane at 0 - 20℃; optical yield given as %ee; enantioselective reaction;
96%	Stage #1: 2-Cyclohepten-1-one; diethylzinc With C₄₄H₃₈Fe₂NO₂P; copper(II) bis(trifluoromethanesulfonate) In toluene at -30℃; for 3h; Inert atmosphere; Stage #2: With ammonium chloride In water; toluene optical yield given as %ee; enantioselective reaction;

96%	With C₂₂H₂₇AgClN₃O₂; copper(II) bis(trifluoromethanesulfonate) In tetrahydrofuran at 0 - 20℃; for 3h; optical yield given as %ee; enantioselective reaction;	4.3. General procedure for the Cu(OTf)₂-catalyzed ECA of enone with R₂Zn General procedure: To a solution of azolium salt (0.045 mmol) in THF (9 mL) were added Cu(OTf)2 (0.045 mmol) and enone (1 mmol). After the mixture was cooled to 0 °C, Et2Zn (3 mmol, 1 mol/L in hexanes) was added to the reaction vessel. The color immediately changed from yellow to dark brown. After stirring at room temperature for 3 h, the reaction was quenched with 10% HCl aq. The resulting mixture was extracted with diisopropyl ether and dried over Na2SO4. The product was purified by silica gel column chromatography (hexane/EtOAc). The ee was measured by chiral GLC.
95%	With (S)-(+)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)-bis-[(1R)-1-phenethyl]amine; copper(II) bis(trifluoromethanesulfonate) In toluene at -30℃; for 18h;
94%	In toluene at -20℃; for 3h;
67%	With copper(II) bis(trifluoromethanesulfonate); (S)-TfNH-CH(t-Bu)-CH₂-PPh₂ In dichloromethane at 23℃; for 3h;
	With copper(II) bis(trifluoromethanesulfonate); (11aR)-(+)-10,11,12,13-tetrahydrodiindeno[7,1-de:1', 7'-fg][1,3,2]dioxaphosphocin-5-bis[(R)-1-phenylethyl]amine In toluene at 0℃; for 2h;
91.9 - 95.3 % ee	Stage #1: at 20℃; for 0.333333h; Stage #2: 2-Cyclohepten-1-one; diethylzinc In toluene at -30 - 23℃;	78; 79 All reactions at room temperature were performed using a Miniblock XT parallel synthesis reactor. The reactions at low temperatures were carried out individually. In a 20 ml reaction tube, a mixture of Cu(OTf)2 (1.8 mg, 5µmol) and a phosphoramidite ligand (11µmol) in a degassed solvent (5 ml) was stirred at room temperature for 20min. To this mixture, Et2Zn (1.1M in toluene, 1.4 ml) and a cycloalkenone (1.0 mmol) were added at a given temperature (-30°C or 23°C). The mixture was stirred at the same temperature for 4h. The reaction was quenched with 1N HCl. The aqueous layer was extracted with Et2O. The combined extracts were washed with brine and dried over MgSO4. The crude product was filtered through a short silica gel column and subjected to 1H NMR and GC analysis using a Supelco Beta Dex 225 column. The absolute configuration was determined by chiral GC analysis in comparison with authentic samples. The results are summarized in Tables 8-10.
97.5 % ee	Stage #1: at 20℃; for 0.333333h; Stage #2: 2-Cyclohepten-1-one; diethylzinc In toluene at -30℃;	80 All reactions at room temperature were performed using a Miniblock XT parallel synthesis reactor. The reactions at low temperatures were carried out individually. In a 20 ml reaction tube, a mixture of Cu(OTf)2 (1.8 mg, 5µmol) and a phosphoramidite ligand (11µmol) in a degassed solvent (5 ml) was stirred at room temperature for 20min. To this mixture, Et2Zn (1.1M in toluene, 1.4 ml) and a cycloalkenone (1.0 mmol) were added at a given temperature (-30°C or 23°C). The mixture was stirred at the same temperature for 4h. The reaction was quenched with 1N HCl. The aqueous layer was extracted with Et2O. The combined extracts were washed with brine and dried over MgSO4. The crude product was filtered through a short silica gel column and subjected to 1H NMR and GC analysis using a Supelco Beta Dex 225 column. The absolute configuration was determined by chiral GC analysis in comparison with authentic samples. The results are summarized in Tables 8-10.

Reference： [1]Liang, Liang; Au-Yeung, Terry T.-L.; Chan, Albert S. C. [Organic Letters, 2002, vol. 4, # 22, p. 3799 - 3801]
[2]Location in patent: experimental part Shibata, Naoatsu; Okamoto, Masaki; Yamamoto, Yuko; Sakaguchi, Satoshi [Journal of Organic Chemistry, 2010, vol. 75, # 16, p. 5707 - 5715]
[3]Zou, Dong-Yun; Duan, Zheng-Chao; Hu, Xiang-Ping; Zheng, Zhuo [Tetrahedron Asymmetry, 2009, vol. 20, # 2, p. 235 - 239]
[4]Location in patent: experimental part Yoshimura, Misato; Shibata, Naoatsu; Kawakami, Miaki; Sakaguchi, Satoshi [Tetrahedron, 2012, vol. 68, # 17, p. 3512 - 3518]
[5]Naasz, Robert; Arnold, Leggy A.; Pineschi, Mauro; Keller, Erik; Feringa, Ben L. [Journal of the American Chemical Society, 1999, vol. 121, # 5, p. 1104 - 1105]
[6]Zhang, Weicheng; Wang, Chun-Jiang; Gao, Wenzhong; Zhang, Xumu [Tetrahedron Letters, 2005, vol. 46, # 36, p. 6087 - 6090]
[7]Krauss, Isaac J.; Leighton, James L. [Organic Letters, 2003, vol. 5, # 18, p. 3201 - 3203]
[8]Zhou, Hai; Wang, Wen-Hu; Fu, Yu; Xie, Jian-Hua; Shi, Wen-Jian; Wang, Li-Xin; Zhou, Qi-Lin [Journal of Organic Chemistry, 2003, vol. 68, # 4, p. 1582 - 1584]
[9]Current Patent Assignee: Mitsubishi Chemical Corp (in: MCHC Group); MITSUBISHI CHEMICAL HOLDINGS CORPORATION; STATE UNIVERSITY OF NEW YORK - WO2004/76464, 2004, A2 Location in patent: Page/Page column 74; 75
[10]Current Patent Assignee: Mitsubishi Chemical Corp (in: MCHC Group); MITSUBISHI CHEMICAL HOLDINGS CORPORATION; STATE UNIVERSITY OF NEW YORK - WO2004/76464, 2004, A2 Location in patent: Page/Page column 74; 75

17
[ 1121-66-0 ]
[ 160878-96-6 ]

Yield	Reaction Conditions	Operation in experiment
89%	With pyridine; iodine at 0 - 20℃; for 16h;
59%	With pyridine; iodine In dichloromethane at 0 - 20℃; Inert atmosphere;
55%	With 4-dimethylaminopyridine; iodine; potassium carbonate In tetrahydrofuran; lithium hydroxide monohydrate at 20℃; for 4h;

52%	With 4-dimethylaminopyridine; iodine; potassium carbonate In tetrahydrofuran; lithium hydroxide monohydrate at 20℃; for 2h; Inert atmosphere;
50%	With 4-dimethylaminopyridine; iodine; potassium carbonate In tetrahydrofuran for 24h;
47%	With pyridine; iodine In Carbon tetrachloride
	With pyridine; iodine In dichloromethane at 0 - 20℃; for 2h;
	With 4-dimethylaminopyridine; iodine; potassium carbonate In tetrahydrofuran; lithium hydroxide monohydrate at 20℃; for 2h;

Reference： [1]Sunden, Henrik; Ma, Jian-Nong; Hansen, Lars K.; Gustavsson, Anna-Lena; Burstein, Ethan S.; Olsson, Roger [ChemMedChem, 2013, vol. 8, # 8, p. 1283 - 1294]
[2]Sundén, Henrik; Schäfer, Anja; Scheepstra, Marcel; Leysen, Seppe; Malo, Marcus; Ma, Jian-Nong; Burstein, Ethan S.; Ottmann, Christian; Brunsveld, Luc; Olsson, Roger [Journal of Medicinal Chemistry, 2016, vol. 59, # 3, p. 1232 - 1238]
[3]Chen, Yu; Gardiner, Michael G.; Lan, Ping; Banwell, Martin G. [Journal of Organic Chemistry, 2022, vol. 87, # 9, p. 6146 - 6160]
[4]Frison, Gilles; Guinchard, Xavier; Marinetti, Angela; Retailleau, Pascal; Smal, Vitalii; Voituriez, Arnaud; Zhang, Zhenhao [Journal of the American Chemical Society, 2020, vol. 142, # 8, p. 3797 - 3805]
[5]Krafft, Marie E.; Cran, John W. [Synlett, 2005, # 8, p. 1263 - 1266]
[6]Mayasundari, Anand; Young, David G.J. [Tetrahedron Letters, 2001, vol. 42, # 2, p. 203 - 206]
[7]Praveen, Chandrasekar; Perumal, Paramasivan T. [Cuihua Xuebao/Chinese Journal of Catalysis, 2016, vol. 37, # 2, p. 288 - 299]
[8]Lan, Yu; Liu, Jia-Bin; Lu, Liang-Qiu; Shi, Bin; Wang, Liang; Wang, Ze-Tian; Xiao, Wen-Jing [Angewandte Chemie - International Edition, 2022, vol. 61, # 24][Angew. Chem., 2022, vol. 134, # 24]

18
[ 1121-66-0 ]
[ 108-59-8 ]
[ 287493-82-7 ]

Yield	Reaction Conditions	Operation in experiment
97%	With (R,R)-La-linked-BINOL Complex In 1,2-dimethoxyethane at 4℃; for 85h;
97%	In 1,2-dimethoxyethane at 4℃; for 85h;
75%	In <i>tert</i>-butyl alcohol at 30℃; for 72h;	15 Example 15; Production of (R)-3-[bis(methoxycarbonyl)methyl] cycloheptanone Under an atmosphere of argon, 11.0 mg (0.02 mmol, S/C = 100) of Ru[(S,S)-Msdpen] (hexamethylbenzene). 111 L (1.0 mmol) of 2-cycloheptenone, 114 L (1.0 mmol) of dimethyl malonate, and 1 mL of 2-methyl-2-propanol were placed in a 20 mL Schlenk tube and stirred at 30C for 72 hours. This solution was purified by flash column chromatography (hexane/acetone = 90/10, SiO2) to give 181 mg (75% yield) of the title compound. The optical rotation [?]D27 was +45.2 (c 1.76, CHCl3). This was reacted with (2R,3R)-butanediol in the presence of a catalytic amount of p-toluenesulfonic acid so as to be converted into a ketal derivative. The 13C NMR spectrum of this derivative was measured, and the optical purity was determined from the ratio of the integrals of the peaks of two diastereomers, with the result that it was >99 %ee.

70%

In tetrahydrofuran at 4℃; for 72h;

Reference： [1]Kim, Yun Sik; Matsunaga, Shigeki; Das, Jagattaran; Sekine, Akihiro; Ohshima, Takashi; Shibasaki, Masakatsu [Journal of the American Chemical Society, 2000, vol. 122, # 27, p. 6506 - 6507]
[2]Matsunaga, Shigeki; Ohshima, Takashi; Shibasaki, Masakatsu [Advanced Synthesis and Catalysis, 2002, vol. 344, # 1, p. 3 - 15]
[3]Current Patent Assignee: KANTO KAGAKU HOLDINGS K.K. - EP1439159, 2004, A1 Location in patent: Page 22
[4]Matsunaga; Ohshima; Shibasaki [Tetrahedron Letters, 2000, vol. 41, # 44, p. 8473 - 8478]

19
[ 502-41-0 ]
[ 1121-66-0 ]

Yield	Reaction Conditions	Operation in experiment
83%	With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In fluorobenzene; dimethyl sulfoxide at 60℃; for 4h;
82%	With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In fluorobenzene; dimethyl sulfoxide at 65℃; for 6h;
78%	With 1-n-butyl-3-methylimidazolim bromide; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione at 75℃; for 8h;

Reference： [1]Nicolaou; Zhong; Baran [Journal of the American Chemical Society, 2000, vol. 122, # 31, p. 7596 - 7597]
[2]Nicolaou; Montagnon; Baran; Zhong [Journal of the American Chemical Society, 2002, vol. 124, # 10, p. 2245 - 2258]
[3]Chhikara, Bhupender S.; Chandra, Ramesh; Tandon, Vibha [Tetrahedron Letters, 2004, vol. 45, # 41, p. 7585 - 7588]

20
[ 7766-51-0 ]
[ 1121-66-0 ]
[ 544-97-8 ]
[ 329324-91-6 ]

Yield	Reaction Conditions	Operation in experiment
131.0 mg	Stage #1: 2-Cyclohepten-1-one; dimethyl zinc(II) With copper(I) trifluoromethanesulfonate benzene; 2-(diphenylphosphino)-phenyl-L-Val-L-Phe-Bu In toluene at -20℃; for 24h; Stage #2: 4-iodobut-1-ene With N,N,N,N,N,N-hexamethylphosphoric triamide In toluene at 0℃; for 48h; Further stages.;

Reference： [1]Degrado; Mizutani; Hoveyda [Journal of the American Chemical Society, 2001, vol. 123, # 4, p. 755 - 756]

21
[ 1121-66-0 ]
[ 544-97-8 ]
(S)-(-)-3-methylcycloheptan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	Stage #1: dimethyl zinc(II) With copper acetylacetonate; 1-[3-((S)-1-hydroxy-2-butanylamino)-3-oxopropyl]-3-methylbenzimidazolium iodide; caesium carbonate In tetrahydrofuran; hexane at 20℃; for 0.25h; Stage #2: 2-Cyclohepten-1-one In tetrahydrofuran; hexane at 20℃; for 27h; optical yield given as %ee;
96%	Stage #1: dimethyl zinc(II) With copper(I) trifluoromethanesulfonate benzene; C₂₁H₂₆AgIN₃O₂ In tetrahydrofuran at 20℃; for 0.5h; Stage #2: 2-Cyclohepten-1-one In tetrahydrofuran at 20℃; for 3h; enantioselective reaction;
96%	Stage #1: dimethyl zinc(II) With copper(I) triflate benzene complex; C₂₁H₂₅AgIN₃O₂ In tetrahydrofuran; hexane at 0 - 20℃; for 0.5h; Stage #2: 2-Cyclohepten-1-one In tetrahydrofuran; hexane at 20℃; for 3h; enantioselective reaction;	4.4. General procedure for method B General procedure: The reaction was performed under open-air conditions.CuOTf.1/2C6H6 (10 mg, 0.04 mmol) and NHC-Ag complex 1b (59 mg, 0.10 mmol, 10 mol %) were added to anhydrous THF(5.5 mL). After stirring at room temperature for 1 h, the mixturewas cooled to 0 °C. Then, Et2Zn (3 mmol, 1 M in hexanes, 3 mL) wasadded to the reaction vessel. After the resulting mixturewas stirredat room temperature for 30 min, a solution of enone 3 (96 mg,1 mmol) in anhydrous THF (1.5 mL) was added dropwise over aperiod of 10 min. The reaction mixture was stirred at room temperaturefor 3 h.

93%	Stage #1: dimethyl zinc(II) With copper(II) bis(trifluoromethanesulfonate); (3,5-Dioxa-4-phospha-cyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)-bis-((R)-1-phenyl-ethyl)-amine In toluene at -25℃; for 0.2h; Inert atmosphere; Stage #2: 2-Cyclohepten-1-one In toluene at -25℃; optical yield given as %ee;
85%	With Cu₂(OTf)2; bis[(S,S)-H₈-BINOL][(R)-BINOL]diphosphite In diethyl ether at -30℃; for 24h;
55%	With (S,E)-N-((4,6-di-tert-butylpyridin-2-yl)methylene)-1-(diphenylphosphino)-3,3-dimethylbutan-2-amine; copper(II) bis(trifluoromethanesulfonate) In dichloromethane at -40℃; for 24h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	4.3. General procedure for the asymmetric 1,4-addition General procedure: A solution of Cu(OTf)2 (0.01 mmol) and ligand (0.025 mmol) in dichloromethane (1.5 mL) was stirred under an argon atmosphere at room temperature for 0.5 h. after which enone (1 mmol) was added to this catalyst solution. The solution was then cooled to -40 °C, then it was stirred at -40 °C for 15 min, after which Et2Zn (1.5 mmol, 0.153 ml) was added slowly. The resulting mixture was stirred at -40 °C for 24 h and then quenched with a 1 M HCl solution (2 mL). After warming the reaction mixture to room temperature, the reaction mixture was extracted with diethyl ether (10 mL × 3). The data of the ee values were determined by chiral-phase GC analysis with a γ-DEX-225 (Supelco) column (30 m x 0.25 mm) or β-DEX-225 (Supelco) column (30 m × 0.25 mm).
	With bis[(R)-1-phenylpropyl]amine based phosphoramidite ligand; Cu(OTf)3 In toluene at -40℃;

Reference： [1]Location in patent: experimental part Shibata, Naoatsu; Yoshimura, Misato; Yamada, Haruka; Arakawa, Ryuichi; Sakaguchi, Satoshi [Journal of Organic Chemistry, 2012, vol. 77, # 8, p. 4079 - 4086]
[2]Matsumoto, Keitaro; Nakano, Yuki; Shibata, Naoatsu; Sakaguchi, Satoshi [RSC Advances, 2016, vol. 6, # 10, p. 7755 - 7759]
[3]Nakano, Yuki; Sakaguchi, Satoshi [Journal of Organometallic Chemistry, 2017, vol. 846, p. 407 - 416]
[4]Casas-Arce, Eva; Ter Horst, Bjorn; Feringa, Ben L.; Minnaard, Adriaan J. [Chemistry - A European Journal, 2008, vol. 14, # 14, p. 4157 - 4159]
[5]Liang, Liang; Au-Yeung, Terry T.-L.; Chan, Albert S. C. [Organic Letters, 2002, vol. 4, # 22, p. 3799 - 3801]
[6]Location in patent: experimental part Ebisu, Yasuhiro; Kawamura, Kenjiro; Hayashi, Masahiko [Tetrahedron Asymmetry, 2012, vol. 23, # 13, p. 959 - 964]
[7]Alexakis; Rosset; Allamand; March; Guillen; Benhaim [Synlett, 2001, # 9, p. 1375 - 1378]

22
[ 1121-66-0 ]
[ 557-20-0 ]
(R)-3-ethylcycloheptan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With chiral binapthol P-N ligand; copper(II) bis(trifluoromethanesulfonate) In toluene
99%	With n-butyllithium; C₂₁H₂₉N₂O⁽¹⁺⁾*F₆P^(1-); copper(II) bis(trifluoromethanesulfonate) In diethyl ether at 20℃; for 1h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
98%	With copper(I) trifluoromethanesulfonate benzene; [(2-PPh₂)C₆H₄CH]-Val-Phe-NH-Bu In toluene at -30℃; for 12h;

98%	Stage #1: 2-Cyclohepten-1-one; diethylzinc With C₄₄H₃₈Fe₂NO₂P; copper(II) bis(trifluoromethanesulfonate) In toluene at -30℃; for 3h; Inert atmosphere; Stage #2: With ammonium chloride In water; toluene optical yield given as %ee; enantioselective reaction;
51%	With copper(I) thiophene-2-carboxylate; 2-(diphenylphosphanyl)-N-{(S)-2-methyl-1-[(S)-4-phenyl-4,5-dihydrooxazol-2-yl]propyl}benzamide In hexane; toluene at -35℃; for 4h; Inert atmosphere; Schlenk technique; enantioselective reaction;
40%	Stage #1: diethylzinc With N,N-bis-((S)-1-phenylethyl)-(R)-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine; C₈H₁₂CuN₄⁽¹⁺⁾C₂F₃O₂^(1-)C₂HF₃O₂ In diethyl ether; dichloromethane; toluene for 0.166667h; Stage #2: 2-Cyclohepten-1-one In diethyl ether; dichloromethane; toluene at -78℃; for 2h;
	With chiral biphenol-based phosphoramidite ligand In diethyl ether; hexane at -30℃; for 12h;
	With copper(I) thiophene-2-carboxylate; C₃₈H₃₀F₆NP In diethyl ether; hexane at -30℃; for 24h; optical yield given as %ee; enantioselective reaction;
97 %Chromat.	Stage #1: 2-Cyclohepten-1-one; diethylzinc With C₅₂H₆₀O₁₀P₂; copper(II) trifluoroacetate In hexane; toluene at -20℃; for 12h; Inert atmosphere; Stage #2: With hydrogenchloride In hexane; water; toluene optical yield given as %ee; enantioselective reaction;

Reference： [1]Alexakis; Benhaim; Rosset; Humam [Journal of the American Chemical Society, 2002, vol. 124, # 19, p. 5262 - 5263]
[2]Location in patent: scheme or table Rix, Diane; Labat, Stephane; Toupet, Loic; Crevisy, Christophe; Mauduit, Marc [European Journal of Inorganic Chemistry, 2009, # 13 SPEC. ISS., p. 1989 - 1999]
[3]Degrado; Mizutani; Hoveyda [Journal of the American Chemical Society, 2001, vol. 123, # 4, p. 755 - 756]
[4]Zou, Dong-Yun; Duan, Zheng-Chao; Hu, Xiang-Ping; Zheng, Zhuo [Tetrahedron Asymmetry, 2009, vol. 20, # 2, p. 235 - 239]
[5]Shin, Minkyeong; Gu, Minji; Lim, Sung Soo; Kim, Min-Jae; Lee, JuHyung; Jin, HyeongGyu; Jang, Yun Hee; Jung, Byunghyuck [European Journal of Organic Chemistry, 2018, vol. 2018, # 24, p. 3122 - 3130]
[6]Lewis, William; Nouch, Ryan; Robinson, David; Willcox, Darren; Woodward, Simon [Organometallics, 2020]
[7]Alexakis, Alexandre; Polet, Damien; Benhaim, Cyril; Rosset, Stephane [Tetrahedron Asymmetry, 2004, vol. 15, # 14, p. 2199 - 2203]
[8]Palais, Laetitia; Alexakis, Alexandre [Chemistry - A European Journal, 2009, vol. 15, # 40, p. 10473 - 10485]
[9]Location in patent: experimental part Zhao, Qing-Lu; Wang, Lai-Lai; Xing, Ai-Ping [Tetrahedron Asymmetry, 2010, vol. 21, # 24, p. 2993 - 2998]

23
[ 1121-66-0 ]
[ 73183-34-3 ]
[ 350498-94-1 ]

Yield	Reaction Conditions	Operation in experiment
95%	With NaO(t-Bu); (R,S)-Taniaphos; CuCl In methanol; tetrahydrofuran CuCl (2 mol), NaO(t-Bu) (3 mol %), (R,S)-Taniaphos (4 mmol %), MeOH (2 equiv.), room temp., 24 h;
93%	With sodium t-butanolate; 1,3-bis(cyclohexyl)imidazolium tetrafluoroborate In tetrahydrofuran at 22℃; for 1h; N₂ atmosphere;
93%	With N,N'-dicyclohexylimidazolium tetrafluoroborate In tetrahydrofuran 2.5 mol% imidazolium salt, THF, 22°C, 1.0 h, N2 atm.; aq. workup;

91%	With 2-((1,3-bis(N-butylimidazol-2-ylidene)phenylene)(dimethylamido)bis(iodo))rhodium(III); 2-((1,3-bis(N-butylimidazol-2-ylidene)phenylene)(dimethylamido)bis(chloro))rhodium(III) In methanol at 22℃; for 1h; Sealed tube;	4.5 General procedure for catalyses General procedure: A 1 dram vial containing a magnetic stir bar was charged with α,β-unsaturated compound (0.0735mmol), bis(pinacolato)diboron (0.184mmol), pre-catalyst A (2.00mg, 2.94μmol), and solvent (0.700mL). The vial was closed and stirred vigorously for 1h at 22°C during which time a dark precipitate was observed to form. After 1h, a 10μL aliquot was passed through a short plug of celite and a 0.45 um PTFE filter. It was injected into the GC-MS to determine conversion. The crude reaction mixture was then filtered through a plug of celite. Volatiles were then removed under reduced pressure resulting in an oil. 1H NMR and HRMS was taken of the crude product to confirm the borylated product. The crude product was then purified by silica gel chromatography to determine an isolated yield.
86%	In toluene carbonyl compound in toluene was added to bis(pinacolato)dibotane(4) and(Pt(PPh3)4) and stirred overnight at 110°C; toluene was removed under vac., mixt. was washed with water and extd. with pentane, extract was dried over MgSO4, pentane was removed under vac., product was purified by chromy. on silica (10% Et2O-petroleum ether); elem. anal.;
82%	With potassium acetate; copper(l) chloride In N,N-dimethyl-formamide at 20℃; for 16h;
75%	With Wilkinson's catalyst In toluene at 80℃; for 12h;
	With potassium acetate; copper(l) chloride; lithium chloride In N,N-dimethyl-formamide

Reference： [1]Feng, Xinhui; Yun, Jaesook [Chemical Communications, 2009, # 43, p. 6577 - 6579]
[2]Lee, Kang-sang; Zhugralin, Adil R.; Hoveyda, Amir H. [Journal of the American Chemical Society, 2009, vol. 131, p. 7253 - 7255]
[3]Lee, Kang-sang; Zhugralin, Adil R.; Hoveyda, Amir H. [Journal of the American Chemical Society, 2009, vol. 131, p. 7253 - 7255]
[4]Reilly, Sean W.; Akurathi, Gopalakrishna; Box, Hannah K.; Valle, Henry U.; Hollis, T. Keith; Webster, Charles Edwin [Journal of Organometallic Chemistry, 2016, vol. 802, p. 32 - 38]
[5]Ali, Hijazi Abu; Goldberg, Israel; Srebnik, Morris [Organometallics, 2001, vol. 20, # 18, p. 3962 - 3965]
[6]Takahashi, Kou; Ishiyama, Tatsuo; Miyaura, Norio [Journal of Organometallic Chemistry, 2001, vol. 625, # 1, p. 47 - 53]
[7]Kabalka, George W.; Das, Bhaskar C.; Das, Sasmita [Tetrahedron Letters, 2002, vol. 43, # 13, p. 2323 - 2325]
[8]Kabalka, George W.; Das, Bhaskar C.; Das, Sasmita [Tetrahedron Letters, 2001, vol. 42, # 41, p. 7145 - 7146]

24
[ 1121-66-0 ]
[ 27571-04-6 ]

Yield	Reaction Conditions	Operation in experiment
83%	With tert.-butylhydroperoxide; Rh₂(Cap)4; potassium carbonate In dichloromethane at 40℃; for 3h;
82%	With tert.-butylhydroperoxide; potassium carbonate In dichloromethane at 24℃; for 60h;

Reference： [1]Catino, Arthur J.; Forslund, Raymond E.; Doyle, Michael P. [Journal of the American Chemical Society, 2004, vol. 126, # 42, p. 13622 - 13623]
[2]Yu, Jin-Quan; Corey [Journal of the American Chemical Society, 2003, vol. 125, # 11, p. 3232 - 3233]

25
[ 1121-66-0 ]
[ 2051-90-3 ]
8,8-diphenylbicyclo[5.1.0]octan-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	With tetrabutylammomium bromide; copper(I) bromide In pyridine; N,N-dimethyl-formamide at -10 - -5℃; Electrochemical reaction;

Reference： [1]Oudeyer, Sylvain; Léonel, Eric; Paugam, Jean Paul; Nédélec, Jean-Yves [Tetrahedron, 2003, vol. 59, # 7, p. 1073 - 1081]

26
[ 1121-66-0 ]
[ 15014-25-2 ]
(S)-3-[bis(benzyloxycarbonyl)methyl]cycloheptanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: 2-Cyclohepten-1-one; malonic acid dibenzyl ester With 1,1,1,3',3',3'-hexafluoro-propanol; (S,S)-La-linked-BINOL at -78℃; for 0.0833333h; Stage #2: at 20℃; for 30h;
69%	With C₅₉H₈₆N₁₀O₉; benzoic acid In tetrahydrofuran at 40℃; for 96h; Sealed tube; enantioselective reaction;
61%	With H-(L-Leu)<SUB>2</SUB>-Ac<SUB>5</SUB>c-(L-Leu)<SUB>4</SUB>-OMe In tetrahydrofuran at 40℃; for 120h; enantioselective reaction;	General procedure for Michael addition reaction. General procedure: Dialkyl malonate (0.300 mmol, 3 equiv) was added to the stirred solution of cyclic enone (0.100 mmol) and peptide (0.005-0.020 mmol, 5-20 mol %) in solvent (0.4 M) at room temperature, and the reaction mixture was stirred appropriate time at 30 or 40 °C. After removal of solvent, the residue was purified by flash column chromatography on silica gel.

Reference： [1]Takita, Ryo; Ohshima, Takashi; Shibasaki, Masakatsu [Tetrahedron Letters, 2002, vol. 43, # 26, p. 4661 - 4665]
[2]Ueda, Atsushi; Umeno, Tomohiro; Doi, Mitsunobu; Akagawa, Kengo; Kudo, Kazuaki; Tanaka, Masakazu [Journal of Organic Chemistry, 2016, vol. 81, # 15, p. 6343 - 6356]
[3]Umeno, Tomohiro; Ueda, Atsushi; Doi, Mitsunobu; Kato, Takuma; Oba, Makoto; Tanaka, Masakazu [Tetrahedron Letters, 2019, vol. 60, # 49]

27
[ 1121-66-0 ]
[ 98-80-6 ]
(R)-3-Phenyl-cycloheptanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With triethylamine In 1,4-dioxane; water at 25℃; for 2h;	5.7 [Table 2]1,4-Addition of arylboronic acid to alpha, beta-unsaturated carbonyl compounds Carbonyl compound employed ArB(OH)2 (X=) [RhCl(coe)2]2/KOH[a] [Rh(nbd)2]BF4/NEt3[b] yield/%[c] yield/%[c] %ee[d] 1 2-cyclopentenone 3-Cl 53 87 99 96 2 4-MeO - - 99 96 3 2-cyclohexenone H 84 98 99 99.6 [e] 4 3-MeO 77 99 90 99.5 5 5 4-MeO 88 98 99 99.8 6 3-Cl 95 98 86 99.8 7 2-cycloheptenone H 48 90 90 98 8 (E)-C5H11CH=CHCOCH3 H 84 67 87 (42[f]) 74 (84[f]) 9 H - - 99 5[g] 10 H - - trace -[h] 11 3-MeO 99 67 98 (65[f])) 80 (83[f] 12 3-MeO (80 C) 98 71 - - 13 3-F 89 75 97 81 14 (E)-i-C3H7CH=CHCOCH3 H 72 88 80 92 [i] 15 3-MeO 80 86 78 94[j] 16 3-F 66 81 71 90[j] 17 (E)-cyclo-C6H11CH=CHCOCH3 3-MeO - - 81 86 [k] 18 (E)-i-C3H7CH=CHCO-cyclo-C6H11 3-MeO - - 62 81 19 (E)-C5H11CH=CHCOC6H5 3-MeO - - 91 85 20 (E)-i-C3H7CH=CHCOC6H5 3-MeO - - 98 85 [i] 21 (E)-C6H5CH=CHCOCH3 3-MeO - - 99 78 22 (E)-C6H5CH=CHCOC6H5 3-MeO - - 98 66[i] 23 (E)-naphthyl-CH=CHCOCH3 3-MeO - - 93 89[l] 24 (Z)-C3H7CH=CHCOC2H5 3-MeO - - 64 1 25 (Z)-C3H7CH=CHCOCH(C2H5)C2H5 3-MeO - - 69 10[i] 26 (E)-C6H5CH=CHCO2Et 3-MeO - - 48 65[m] 27 (E)-CH3CH=CHCO2Me 3-MeO - - 57 75[m] 28 (E)-CH3CH=CHCO2Et 3-MeO 94 56 - - 29 (E)-CH3CH=CHCO2iPr 3-MeO 90 57 33 70[m] 30 (E)-CH3CH=CHCHO 3-MeO 47 41 60 68[i] 31 (E)-C6H5CH=CHCHO 3-MeO - - 16 92[i] 32 5H-furan-2-one H - - 68 77[i] 33 5,6-dihydro-2H-pyran-2-one H - - 72 89[i] 34 5,6-dihydro-2H-pyran-2-one 3-MeO - - 61 91[n] 35 (E)-CH3CH=CHCONCH2C6H5 3-MeO 43 63[o] - - [a] The reaction was conducted in dioxane (2.6 mL) and H2O (0.43 mL) in the presence of enone (1 mmol), arylboronic acid (1.5 mmol), [RhCl(coe)2]2 (3 mol%, based on Rh), Compound 8 (3.3 mol%), and KOH (1 mmol) for 16 hours at 50 C. [b] The reaction was conducted in dioxane (2.6 mL) and H2O (0.43 mL) in the presence of enone (1 mmol), arylboronic acid (1.5 mmol), [Rh(nbd)2]BF4 (3 mol%, based on Rh), Compound 8 (3.3 mol%), and NEt3 (1 mmol) for 2 hours at 25 C. [c] Isolation yield, based on enone [d] HPLC analysis employed Dicel Chiralcel. [e] 0.5 h at 25 C. [f] 48 h at 5 C. [g] Compound 9 employed. [h] Compound 10 employed [i] 6 h at 25 C. [j] 16 h at 25 C. [k] 2.5 equivalent of arylboronic acid employed; 10 h at 25 C. [l] 3 h at 25 C. [m] 24 h at 25 C. [n] 12 h at 25 C. [o] Using K2HPO4 as base.
88%	With bis(ethylene)rhodium acetylacetonate; (S)-P-Phos In 1,4-dioxane; water at 100℃; for 5h;
83%	With acetylacetonatobis(ethylene)rhodium(I); (R)-6,6'-dimethoxy-P₂,P₂,P₂',P₂'-tetrakis-[3-(carbonyloxy)phenyl]biphenyl-2,2'-bisphosphine sodium salt; sodium carbonate In water at 100℃; enantioselective reaction;

48%	With potassium hydroxide In 1,4-dioxane; water at 50℃; for 16h;	5.7 [Table 2]1,4-Addition of arylboronic acid to alpha, beta-unsaturated carbonyl compounds Carbonyl compound employed ArB(OH)2 (X=) [RhCl(coe)2]2/KOH[a] [Rh(nbd)2]BF4/NEt3[b] yield/%[c] yield/%[c] %ee[d] 1 2-cyclopentenone 3-Cl 53 87 99 96 2 4-MeO - - 99 96 3 2-cyclohexenone H 84 98 99 99.6 [e] 4 3-MeO 77 99 90 99.5 5 5 4-MeO 88 98 99 99.8 6 3-Cl 95 98 86 99.8 7 2-cycloheptenone H 48 90 90 98 8 (E)-C5H11CH=CHCOCH3 H 84 67 87 (42[f]) 74 (84[f]) 9 H - - 99 5[g] 10 H - - trace -[h] 11 3-MeO 99 67 98 (65[f])) 80 (83[f] 12 3-MeO (80 C) 98 71 - - 13 3-F 89 75 97 81 14 (E)-i-C3H7CH=CHCOCH3 H 72 88 80 92 [i] 15 3-MeO 80 86 78 94[j] 16 3-F 66 81 71 90[j] 17 (E)-cyclo-C6H11CH=CHCOCH3 3-MeO - - 81 86 [k] 18 (E)-i-C3H7CH=CHCO-cyclo-C6H11 3-MeO - - 62 81 19 (E)-C5H11CH=CHCOC6H5 3-MeO - - 91 85 20 (E)-i-C3H7CH=CHCOC6H5 3-MeO - - 98 85 [i] 21 (E)-C6H5CH=CHCOCH3 3-MeO - - 99 78 22 (E)-C6H5CH=CHCOC6H5 3-MeO - - 98 66[i] 23 (E)-naphthyl-CH=CHCOCH3 3-MeO - - 93 89[l] 24 (Z)-C3H7CH=CHCOC2H5 3-MeO - - 64 1 25 (Z)-C3H7CH=CHCOCH(C2H5)C2H5 3-MeO - - 69 10[i] 26 (E)-C6H5CH=CHCO2Et 3-MeO - - 48 65[m] 27 (E)-CH3CH=CHCO2Me 3-MeO - - 57 75[m] 28 (E)-CH3CH=CHCO2Et 3-MeO 94 56 - - 29 (E)-CH3CH=CHCO2iPr 3-MeO 90 57 33 70[m] 30 (E)-CH3CH=CHCHO 3-MeO 47 41 60 68[i] 31 (E)-C6H5CH=CHCHO 3-MeO - - 16 92[i] 32 5H-furan-2-one H - - 68 77[i] 33 5,6-dihydro-2H-pyran-2-one H - - 72 89[i] 34 5,6-dihydro-2H-pyran-2-one 3-MeO - - 61 91[n] 35 (E)-CH3CH=CHCONCH2C6H5 3-MeO 43 63[o] - - [a] The reaction was conducted in dioxane (2.6 mL) and H2O (0.43 mL) in the presence of enone (1 mmol), arylboronic acid (1.5 mmol), [RhCl(coe)2]2 (3 mol%, based on Rh), Compound 8 (3.3 mol%), and KOH (1 mmol) for 16 hours at 50 C. [b] The reaction was conducted in dioxane (2.6 mL) and H2O (0.43 mL) in the presence of enone (1 mmol), arylboronic acid (1.5 mmol), [Rh(nbd)2]BF4 (3 mol%, based on Rh), Compound 8 (3.3 mol%), and NEt3 (1 mmol) for 2 hours at 25 C. [c] Isolation yield, based on enone [d] HPLC analysis employed Dicel Chiralcel. [e] 0.5 h at 25 C. [f] 48 h at 5 C. [g] Compound 9 employed. [h] Compound 10 employed [i] 6 h at 25 C. [j] 16 h at 25 C. [k] 2.5 equivalent of arylboronic acid employed; 10 h at 25 C. [l] 3 h at 25 C. [m] 24 h at 25 C. [n] 12 h at 25 C. [o] Using K2HPO4 as base.
	With potassium hydroxide; (R)-(-)-(3,5-dioxa-4-phosphacyclohepta[2,1-a:3,4-a']dinaphthalen-4-yl)diethylamine In 1,4-dioxane at 50℃; for 6h; Title compound not separated from byproducts;
	With di(norbornadiene)rhodium(I) tetrafluoroborate; chiral modified linked BINOL derivative; triethylamine In 1,4-dioxane; water at 25℃; for 2h;

Reference： [1]Current Patent Assignee: JAPAN SCIENCE AND TECHNOLOGY AGENCY - EP1854802, 2007, A1 Location in patent: Page/Page column 25-26
[2]Qian, Shi; Xu, Lijin; Li, Xingshu; Jia, Xian; Wang, Ruihu; Au-Yeung, Terry T.-L.; Chan, Albert S. C.; Hayashi, Tamio; Cao, Rong; Hong, Maochum [Tetrahedron Letters, 2003, vol. 44, # 34, p. 6505 - 6508]
[3]Leseurre, Lucie; Le Boucher D'Herouville, Florent; Millet, Anthony; Genêt, Jean-Pierre; Scalone, Michelangelo; Michelet, Véronique [Catalysis Communications, 2015, vol. 69, p. 129 - 132]
[4]Current Patent Assignee: JAPAN SCIENCE AND TECHNOLOGY AGENCY - EP1854802, 2007, A1 Location in patent: Page/Page column 25-26
[5]Iguchi, Yuki; Itooka, Ryoh; Miyaura, Norio [Synlett, 2003, # 7, p. 1040 - 1042]
[6]Yamamoto, Yasunori; Kurihara, Kazunori; Sugishita, Noriyuki; Oshita, Kengo; Piao, Dongguo; Miyaura, Norio [Chemistry Letters, 2005, vol. 34, # 9, p. 1224 - 1225]

28
[ 1121-66-0 ]
[ 108-59-8 ]
[ 568590-04-5 ]

Yield	Reaction Conditions	Operation in experiment
95%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 72h; Molecular sieve;
75%	With Ru[N-(MeSO₂)-(1R,2R)-diphenylethylenediamine]((CH₃)6C₆) In <i>tert</i>-butyl alcohol at 30℃; for 72h;
74%	With H-(L-Leu)<SUB>2</SUB>-Ac<SUB>5</SUB>c-(L-Leu)<SUB>4</SUB>-OMe In tetrahydrofuran at 40℃; for 120h; enantioselective reaction;	General procedure for Michael addition reaction. General procedure: Dialkyl malonate (0.300 mmol, 3 equiv) was added to the stirred solution of cyclic enone (0.100 mmol) and peptide (0.005-0.020 mmol, 5-20 mol %) in solvent (0.4 M) at room temperature, and the reaction mixture was stirred appropriate time at 30 or 40 °C. After removal of solvent, the residue was purified by flash column chromatography on silica gel.

Reference： [1]Puppala, Manohar; Murali, Annamalai; Baskaran, Sundarababu [Chemical Communications, 2012, vol. 48, # 46, p. 5778 - 5780]
[2]Watanabe, Masahito; Murata, Kunihiko; Ikariya, Takao [Journal of the American Chemical Society, 2003, vol. 125, # 25, p. 7508 - 7509]
[3]Umeno, Tomohiro; Ueda, Atsushi; Doi, Mitsunobu; Kato, Takuma; Oba, Makoto; Tanaka, Masakazu [Tetrahedron Letters, 2019, vol. 60, # 49]

29
[ 1121-66-0 ]
[ 100330-50-5 ]
(R)-3-oxo-2-(3-oxocycloheptyl)hept-6-ynoic acid methyl ester [ No CAS ]
[ 646038-22-4 ]

Reference： [1]Journal of the American Chemical Society,2003,vol. 125,p. 15837 - 15845

30
[ 1121-66-0 ]
[ 98-80-6 ]
[ 435269-65-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With chlorobis(ethylene)rhodium(I) dimer; (Sa)-3,5-(CF₃)2-MeOBIPHEP; potassium hydroxide In water; toluene at 20℃; for 7h; Inert atmosphere; optical yield given as %ee; stereoselective reaction;
99%	With chlorobis(ethylene)rhodium(I) dimer; (R)-(+)-[(η⁵-1-bis(3,5-dimethylphenyl)phosphino-2-(3-diphenylphosphino-2-methylpropenyl)cyclopentadienyl-P)]manganese(I) dicarbonyl; potassium hydroxide In 1,4-dioxane; water at 50℃; for 7h; Inert atmosphere; enantioselective reaction;
87%	With potassium phosphate; [RhCl((S,S)^Me₂dbCOT)]₂ In water; toluene at 20℃; Inert atmosphere; Sealed tube; enantioselective reaction;

85%	With O,O'-(S)-(1,1'-dinaphthyl-2,2'-diyl)-N-2-[2,2'-(2-azapropane-1,3-diyl)-1,1'-biphenylyl]phosphoramidite; acetylacetonatobis(ethylene)rhodium(I) In water; toluene at 45℃; for 0.5h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	4.3. Asymmetric addition of phenylboronic acid (typical procedure) General procedure: To a solution of Rh(acac)(eth)2 (3.8 mg, 0.015 mmol) and phosphoramidite (S)-L1 (19 mg, 0.037 mmol) in 2 mL of toluene, 0.2 mL of water was added and the mixture was stirred for 5 min. at room temperature, under a nitrogen athmosphere. Phenylboronic acid (202 mg, 1.66 mmol) was added and the mixture was heated to 45 °C. Then, freshly distilled 2-cyclohexenone (0.050 mL, 0.5 mmol) was added and the resulting mixture was stirred for 30 min. After cooling to room temperature, the mixture was quenched with a saturated sodium bicarbonate solution and extracted with diethyl ether. The organic phase was dried over sodium sulfate, filtered and the solvent was evaporated. The crude product was purified by column chromatography (SiO2, petroleum ether/diethyl ether 7/3).
84%	With acetylacetonatobis(ethylene)rhodium(I); (S)-BICMAP In 1,4-dioxane; water at 100℃; for 5h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	General procedure for the rhodium(I)-catalyzed asymmetric 1,4-addition to cyclic enones using (S)-(-)-1 General procedure: To a mixture of aryl- or alkenylboronic acid (2.0 mmol), Rh(acac)(C2H4)2 (3.09 mg, 12.0 μmol), and (S)-(-)-1 (8.08 mg, 13.3 μmol) in a dioxane (1.0 mL) and H2O (0.1 mL) was added cyclic enone (0.40 mmol) at room temperature under an Ar atmosphere. The reaction mixture was stirred for 5 h at 100 °C. After being cooled to room temperature, the mixture was quenched with sat. NaHCO3 aq and diluted with EtOAc. The organic layer was washed with water and brine, and dried over Na2SO4. The filtrate was concentrated with a rotary evaporator and the residue was purified by column chromatography (elution with n-hexane/EtOAc = 15-6/1).
80%	With acetylacetonatobis(ethylene)rhodium(I); C₂₇H₂₅FeP In 1,4-dioxane; water at 100℃; for 18h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
76%	With C₄₄H₄₀Cl₂O₄Rh₂; potassium hydroxide In 1,4-dioxane; water at 50℃; for 16h; Schlenk technique; Inert atmosphere; enantioselective reaction;
71%	With chlorobis(ethylene)rhodium(I) dimer; potassium phosphate tribasic trihydrate; C₁₉H₂₃NOS In 1,4-dioxane; water at 20℃; for 3h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
53%	With potassium hydroxide; C₄H₈Cl₂Rh; (1S,4R,5R)-2-(2,6-dimethylphenyl)-5-methoxy-1,5-dimethylbicyclo[2.2.2]octa-2,7-diene In methanol; dichloromethane at 20℃; for 1h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
	With bis(ethylene)rhodium acetylacetonate; (S)-C₂₄H₃₀NO₂P phosphoramidite In 1,4-dioxane; water at 100℃; for 0.333333h;
100 %Chromat.	With chlorobis(ethylene)rhodium(I) dimer; (R)-N-cinnamyl-2-methylpropane-2-sulfinamide; C₇₉H₁₄₆O₂₅; potassium hydroxide In water at 20℃; for 24h; Schlenk technique; Green chemistry; enantioselective reaction;
	With tropos phosphoramidite/rhodium(I) complex

Reference： [1]Location in patent: experimental part Le Boucher D'Herouville, Florent; Millet, Anthony; Scalone, Michelangelo; Michelet, Veronique [Journal of Organic Chemistry, 2011, vol. 76, # 16, p. 6925 - 6930]
[2]Kamikawa, Ken; Tsen, Ya-Yi; Jian, Jia-Hong; Takahashi, Tamotsu; Ogasawara, Masamichi [Journal of the American Chemical Society, 2017, vol. 139, # 4, p. 1545 - 1553]
[3]Melcher, Michaela-Christina; Ivšić, Trpimir; Olagnon, Charlotte; Tenten, Christina; Lützen, Arne; Strand, Daniel [Chemistry - A European Journal, 2018, vol. 24, # 10, p. 2344 - 2348]
[4]Location in patent: experimental part Scafato, Patrizia; Caprioli, Francesca; Rosini, Carlo [Tetrahedron Asymmetry, 2011, vol. 22, # 5, p. 558 - 561]
[5]Mino, Takashi; Hashimoto, Masatoshi; Uehara, Katsunori; Naruse, Yoshiaki; Kobayashi, Shohei; Sakamoto, Masami; Fujita, Tsutomu [Tetrahedron Letters, 2012, vol. 53, # 34, p. 4562 - 4564]
[6]Location in patent: experimental part Csizmadiova, Jana; Meciarova, Maria; Rakovsky, Erik; Horvath, Branislav; sebesta, Radovan [European Journal of Organic Chemistry, 2011, # 30, p. 6110 - 6116]
[7]Sun, Chao; Meng, He; Chen, Chen; Wei, Haili; Ming, Jialin; Hayashi, Tamio [Organic Letters, 2021, vol. 23, # 16, p. 6311 - 6315]
[8]Feng, Xiangqing; Wang, Yazhou; Wei, Beibei; Yang, Jing; Du, Haifeng [Organic Letters, 2011, vol. 13, # 13, p. 3300 - 3303]
[9]Location in patent: experimental part Gendrineau, Thomas; Chuzel, Olivier; Eijsberg, Hendrik; Genet, Jean-Pierre; Darses, Sylvain [Angewandte Chemie - International Edition, 2008, vol. 47, # 40, p. 7669 - 7672]
[10]Boiteau, Jean-Guy; Minnaard, Adriaan J.; Feringa, Ben L. [Journal of Organic Chemistry, 2003, vol. 68, # 24, p. 9481 - 9484]
[11]Khiar, Noureddine; Valdivia, Victoria; Salvador, Alvaro; Chelouan, Ahmed; Alcudia, Ana; Fernandez, Inmaculada [Advanced Synthesis and Catalysis, 2013, vol. 355, # 7, p. 1303 - 1307]
[12]Scafato, Patrizia; Caprioli, Francesca; Pisani, Laura; Padula, Daniele; Santoro, Fabrizio; Mazzeo, Giuseppe; Abbate, Sergio; Lebon, France; Longhi, Giovanna [Tetrahedron, 2013, vol. 69, # 50, p. 10752 - 10762]

31
[ 1121-66-0 ]
[ 13515-95-2 ]
[ 232589-57-0 ]
(S)-2-[3-((2S,3R,4R,5S,6R)-3-Acetylamino-4,5-dihydroxy-6-hydroxymethyl-tetrahydro-pyran-2-ylsulfanyl)-cycloheptylamino]-6-amino-hexanoic acid [ No CAS ]

Reference： [1]Journal of Carbohydrate Chemistry,2003,vol. 22,p. 781 - 800

32
[ 80522-48-1 ]
[ 1121-66-0 ]

Yield	Reaction Conditions	Operation in experiment
74%	With tert.-butylhydroperoxide; disodium hydrogenphosphate; oxygen In dichloromethane at 24℃; for 44h;
	Multi-step reaction with 2 steps 1: trimethylsilyl azide, iodosobenzene / CH₂Cl₂ / 0.25 h / 5 - 25 °C 2: TBAF / CH₂Cl₂; tetrahydrofuran / -5 - 25 °C
	Multi-step reaction with 2 steps 1: PhIO, TMSN₃ / CH₂Cl₂ / -15 °C 2: tetra-n-butylammonium fluoride (TBAF) / tetrahydrofuran / 0 °C

Reference： [1]Yu, Jin-Quan; Wu, Hai-Chen; Corey [Organic Letters, 2005, vol. 7, # 7, p. 1415 - 1417]
[2]Magnus, Philip [Journal of the American Chemical Society, 1998, vol. 120, # 48, p. 12486 - 12499]
[3]Magnus, Philip; Evans, Andrew; Lacour, Jerome [Tetrahedron Letters, 1992, vol. 33, # 21, p. 2933 - 2936]

33
[ 1121-66-0 ]
[ 98-80-6 ]
[ 501919-44-4 ]

Yield	Reaction Conditions	Operation in experiment
99%	With chlorobis(ethylene)rhodium(I) dimer; C₂₂H₂₀N₂O₄; potassium hydroxide In ethanol at 30℃; for 1.5h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
97%	With potassium fluoride; chlorobis(ethylene)rhodium(I) dimer; (R)-1-(tert-butylsulfinyl)-2-(prop-1-en-2-yl)benzene In methanol; dichloromethane; water at 40℃; for 3h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
97%	Stage #1: phenylboronic acid With chlorobis(ethylene)rhodium(I) dimer; (+)-(1R,4R,5R,8R)-4,8-bis(benzyloxy)bicyclo[3.3.1]nona-2,6-diene In tetrahydrofuran at 50℃; for 0.25h; Inert atmosphere; Stage #2: 2-Cyclohepten-1-one With potassium hydroxide In tetrahydrofuran; water at 20℃; for 0.5h; Inert atmosphere; enantioselective reaction;

96%	With potassium hydroxide; chlorobis(ethylene)rhodium(I) dimer; (Ra)-(6,6'-dimethoxybiphenyl-2,2'-diyl)bis[bis(3,4,5-trifluorophenyl)phosphine]; water In toluene at 30℃; for 3h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
94%	With potassium hydroxide; chlorobis(ethylene)rhodium(I) dimer; (1R,4R,7R)-7-isopropyl-2-(1-hydroxy-1-methylethyl)-5-methylbicyclo[2.2.2]octa-2,5-diene In 1,4-dioxane; water at 50℃; for 1h; optical yield given as %ee; enantioselective reaction;
94%	Stage #1: phenylboronic acid With chlorobis(ethylene)rhodium(I) dimer; (+)-(1R,4R,5R,8R)-4,8-bis(3,5-dimethylphenyl)-4,8-dimethoxybicyclo[3.3.1]nona-2,6-diene In tetrahydrofuran at 50℃; for 0.25h; Inert atmosphere; Stage #2: 2-Cyclohepten-1-one With potassium hydroxide In tetrahydrofuran; water at 20℃; for 5h; Inert atmosphere; enantioselective reaction;
92%	With chlorobis(ethylene)rhodium(I) dimer; (R<SUB>S</SUB>)-N-(cinnamyl)-2-methylpropane-2-sulfinamide; potassium hydroxide In methanol; water at 40℃; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
90%	With (R,R)-(−)-2,3-bis(t-butylmethylphosphino)quinoxaline; potassium hydroxide; bis(ethylene)rhodium(I) chloride dimer In 1,4-dioxane at 50℃; for 12h;
90%	Stage #1: In 1,4-dioxane at 20℃; for 0.25h; Stage #2: With potassium hydroxide In tetrahydrofuran; water for 0.25h; Stage #3: 2-Cyclohepten-1-one; phenylboronic acid In tetrahydrofuran; water at 50℃; for 12h;	3 To 1 ml of dioxane were added 1.8 mg (9.0 μmol) of [RhCl(C2H4)2]2 and 3.3 mg (9.9 μmol) of (R,R)-2,3-bis(tert-butylmethylphosphino)quinoxaline (12), and the mixture was stirred at room temperature in a nitrogen atmosphere for 15 minutes. To the reaction mixture was added 0.1 ml of a 1.5 M potassium hydroxide aqueous solution, followed by stirring for 15 minutes. To the mixture were added 0.60 mmol of the organic boronic acid shown in Table 2 below and 0.30 mmol of the β,β-unsaturated carbonyl compound shown in Table 2. After the mixture was stirred at 40° C. for 1 hour, a saturated aqueous solution of sodium hydrogencarbonate was added to stop the reaction. The reaction mixture was extracted five times with ethyl ether, and the organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel thin layer chromatography (hexane/ethyl acetate=3/1). The absolute configuration and the percent ee of the products were determined from the retention time in comparison with the standards.
90%	With chlorobis(ethylene)rhodium(I) dimer; C₁₈H₂₂O₂; potassium hydroxide In 1,4-dioxane; water at 24℃; for 2h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
89%	Stage #1: 2-Cyclohepten-1-one; phenylboronic acid With potassium hydroxide In 1,4-dioxane; water at 40 - 45℃; for 6.5h; Stage #2: With water; sodium hydrogencarbonate In 1,4-dioxane	6 EXAMPLE 6 Asymmetric 1,4-Addition of Organic Boronic Acid to Enone using Rhodium CatalystA solution of 1.9 mg (5.0 μmol) of [Rh(nbd)2]BF4 and 7.5 μmol of (S,S)-1,2-bis((t-butyl)phenylethynylphosphino)ethane (7a) in 1 ml of dioxane was stirred at 40° C. for 15 minutes in a nitrogen atmosphere. To the reaction solution was added 0.1 ml of a 1.5M aqueous solution of potassium hydroxide (0.15 mmol), followed by stirring for 15 minutes. To the reaction mixture were added 1.0 mmol of allylboronic acid 0.50 mmol of an α,β-unsaturated carbonyl compound, followed by aging while stirring at 40° C. for 2 hours. The reaction was quenched by addition of a saturated sodium hydrogencarbonate aqueous solution. The reaction mixture was extracted with diethyl ether five times. The organic layers were combined, washed with a saturated sodium chloride aqueous solution, and filtered. The filtrate was concentrated under reduced pressure. The residue was purified by preparative TLC on silica gel (hexane/ethyl acetate=3/1). The same procedures were repeated, except for replacing 7a as a ligand with each of 7b, 7c, and 7e. The reaction results are shown in Table 1 below.
88%	With potassium hydroxide In 1,4-dioxane at 30℃; for 1h;
87%	With C₂₉H₃₁NO₂PRh; potassium hydroxide In 1,4-dioxane; water at 30℃; for 10h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	4.4.1. General procedure for the rhodium-catalyzed asymmetric 1,4-addition (Table 2 and Table 3) General procedure: At first, KOH (50 μL, 0.10-0.20 mmol; 2.0-4.0 M aqueous) was added to a solution of [RhCl(ligand)]2 (10 μmol Rh), α,β-unsaturated ketone (0.20 mmol), and arylboronic acid (0.22-0.30 mmol) in dioxane (0.50 mL), and the resulting mixture was stirred for 10 h at 30 °C. This was directly passed through a pad of silica gel with EtOAc and the solvent was removed under vacuum. The residue was purified by silica gel preparative TLC with EtOAc/hexane to afford the 1,4-adduct.
87%	With chlorobis(ethylene)rhodium(I) dimer; (S,S)-1,2-bis(ferrocenyl)ethane; potassium hydroxide In water; toluene at 20℃; Inert atmosphere; enantioselective reaction;
84%	With chlorobis(ethylene)rhodium(I) dimer; (R)-[6,6'-bis(bis(3,5-di(trifluoromethyl)phenyl)phosphino)-2,2',3,3'-tetrahydro-5,5'-bibenzo[b][1,4]dioxine]; potassium hydroxide In water; toluene at 20℃; for 18h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
84%	With chlorobis(ethylene)rhodium(I) dimer; (R)-[6,6'-bis(bis(3,5-di(trifluoromethyl)phenyl)phosphino)-2,2',3,3'-tetrahydro-5,5'-bibenzo[b][1,4]dioxine]; potassium hydroxide In water; toluene at 20℃; for 18h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
82%	With acetylacetonatobis(ethylene)rhodium(I); C₄₈H₃₈O₃P₂ In 1,4-dioxane; water at 20 - 100℃; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
80%	Stage #1: phenylboronic acid With triethylamine In water for 0.25h; Inert atmosphere; Stage #2: 2-Cyclohepten-1-one In water at 20℃; for 12h; Inert atmosphere; enantioselective reaction;
52%	Stage #1: phenylboronic acid With chlorobis(ethylene)rhodium(I) dimer; (S)-2-diphenylphosphino-2'-phenylsulfinyl-1,1'-binaphthyl In cyclohexane at 40℃; for 0.333333h; Inert atmosphere; Stage #2: 2-Cyclohepten-1-one With potassium carbonate In cyclohexane; water for 1.5h; enantioselective reaction;	General Procedure for the 1,4-addition of α,β-unsaturated carbonyl compounds with arylboronic acid. General procedure: A flame-dried two-necked flask (10 mL) was charged with ligand(R,Ss)-sulfoxide-MOP L2 (4.2 mg, 7.5 μmol, 1.5 mol%), [Rh(C2H4)2Cl]2 (1.5 mg, 3.8 μmol, 1.5mol% Rh), arylboronic acid 2 (1.0 mmol, 2 equiv), capped with a rubber septum, evacuated andbackfilled with argon (3 cycles), and then added cyclohexane (1.0 mL). After stirring at 40 °C for 20min, α,β-unsaturated carbonyl compound 1 (0.5 mmol) and an degassed aqueous solution of K2CO3(0.1 mL, 2.5 M) was added to the mixture and stirred for the appropriate time (followed by TLCuntil completion). The reaction mixture was directly charged onto a column (silica gel) and flashchromatographed with a mixture of hexane/EtOAc or hexane/Et2O to afford the product 3.

Reference： [1]Liu, Chia-Chen; Janmanchi, Damodar; Chen, Chun-Chih; Wu, Hsyueh-Liang [European Journal of Organic Chemistry, 2012, # 13, p. 2503 - 2507]
[2]Chen, Guihua; Gui, Jiangyang; Li, Liangchun; Liao, Jian [Angewandte Chemie - International Edition, 2011, vol. 50, # 33, p. 7681 - 7685]
[3]Rimkus, Renaldas; Jurgelenas, Marius; Stončius, Sigitas [European Journal of Organic Chemistry, 2015, vol. 2015, # 14, p. 3017 - 3021]
[4]Korenaga, Toshinobu; Osaki, Kazutaka; Maenishi, Ryota; Sakai, Takashi [Organic Letters, 2009, vol. 11, # 11, p. 2325 - 2328]
[5]Okamoto, Kazuhiro; Hayashi, Tamio; Rawal, Viresh H. [Organic Letters, 2008, vol. 10, # 19, p. 4387 - 4389]
[6]Bieliūnas, Vidmantas; Stončius, Sigitas [ChemCatChem, 2021, vol. 13, # 17, p. 3815 - 3823]
[7]Khiar, Noureddine; Salvador, Alvaro; Chelouan, Ahmed; Alcudia, Ana; Fernandez, Inmaculada [Organic and Biomolecular Chemistry, 2012, vol. 10, # 12, p. 2366 - 2368]
[8]Imamoto, Tsuneo; Sugita, Keitaro; Yoshida, Kazuhiro [Journal of the American Chemical Society, 2005, vol. 127, # 34, p. 11934 - 11935]
[9]Current Patent Assignee: CHIBA UNIVERSITY; NIPPON CHEMICAL INDUSTRIAL CO LTD - US2007/21610, 2007, A1 Location in patent: Page/Page column 5
[10]Brown, M. Kevin; Corey [Organic Letters, 2010, vol. 12, # 1, p. 172 - 175]
[11]Current Patent Assignee: CHIBA UNIVERSITY; NIPPON CHEMICAL INDUSTRIAL CO LTD - US2008/221362, 2008, A1 Location in patent: Page/Page column 6-7
[12]Nishimura, Takahiro; Nagaosa, Makoto; Hayashi, Tamio [Chemistry Letters, 2008, vol. 37, # 8, p. 860 - 861]
[13]Location in patent: experimental part Narui, Rintaro; Hayashi, Sayuri; Otomo, Haruka; Shintani, Ryo; Hayashi, Tamio [Tetrahedron Asymmetry, 2012, vol. 23, # 3-4, p. 284 - 293]
[14]Khiar, Noureddine; Salvador, Alvaro; Valdivia, Victoria; Chelouan, Ahmed; Alcudia, Ana; Alvarez, Eleuterio; Fernandez, Inmaculada [Journal of Organic Chemistry, 2013, vol. 78, # 13, p. 6510 - 6521]
[15]Berhal, Farouk; Esseiva, Olivier; Martin, Charles-Henri; Tone, Hitoshi; Genet, Jean-Pierre; Ayad, Tahar; Ratovelomanana-Vidal, Virginie [Organic Letters, 2011, vol. 13, # 11, p. 2806 - 2809]
[16]Location in patent: scheme or table Berhal, Farouk; Wu, Zi; Genet, Jean-Pierre; Ayad, Tahar; Ratovelomanana-Vidal, Virginie [Journal of Organic Chemistry, 2011, vol. 76, # 15, p. 6320 - 6326]
[17]Location in patent: experimental part Yuan, Wei-Cheng; Cun, Lin-Feng; Mi, Ai-Qiao; Jiang, Yao-Zhong; Gong, Liu-Zhu [Tetrahedron, 2009, vol. 65, # 21, p. 4130 - 4141]
[18]Lipshutz, Bruce H.; Isley, Nicholas A.; Moser, Ralph; Ghorai, Subir; Leuser, Helena; Taft, Benjamin R. [Advanced Synthesis and Catalysis, 2012, vol. 354, # 17, p. 3175 - 3179]
[19]Hoshi, Takashi; Fujita, Masataka; Matsushima, Shouta; Hagiwara, Hisahiro; Suzuki, Toshio [Chemistry Letters, 2018, vol. 47, # 6, p. 800 - 802]

34
[ 6414-69-3 ]
[ 1121-66-0 ]
3-(3-oxo-cycloheptyl)-propionic acid ethyl ester [ No CAS ]

Reference： [1]Synlett,2006,p. 309 - 311

35
[ 1121-66-0 ]
[ 185990-03-8 ]
C₁₅H₂₂OSi [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With 1,3-bis-(diphenylphosphino)propane; triethylamine In 1,4-dioxane; water at 50℃; for 16h;
81%	With [(dppp)Rh(cod)]ClO₄; 1,3-bis-(diphenylphosphino)propane; water; triethylamine In 1,4-dioxane at 50℃; Inert atmosphere;

Reference： [1]Walter, Christian; Auer, Gertrud; Oestreich, Martin [Angewandte Chemie - International Edition, 2006, vol. 45, # 34, p. 5675 - 5677]
[2]Location in patent: scheme or table Walter, Christian; Fröhlich, Roland; Oestreich, Martin [Tetrahedron, 2009, vol. 65, # 28, p. 5513 - 5520]

36
[ 1121-66-0 ]
[ 1122-49-2 ]

Yield	Reaction Conditions	Operation in experiment
76%	With bromine; triethylamine In dichloromethane at 0 - 20℃; for 0.666667h; Inert atmosphere;
60%	Stage #1: 2-Cyclohepten-1-one With bromine In dichloromethane at -10℃; for 0.5h; Inert atmosphere; Stage #2: With triethylamine In dichloromethane at -10 - 20℃; for 1.5h; Inert atmosphere;
46%	With bromine In dichloromethane at 0℃;

	Stage #1: 2-Cyclohepten-1-one With bromine In tetrachloromethane at 0℃; for 1h; Stage #2: With triethylamine In tetrachloromethane at 20℃;
	With pyridine; hydrogen bromide; bromine In dichloromethane at 70℃; for 0.5h; Microwave irradiation;

Reference： [1]Almehmadi, Yaseen A.; West [Organic Letters, 2020, vol. 22, # 15, p. 6091 - 6095]
[2]Singh, Kamaljeet; Trinh, Winston; Weaver, Jimmie D. [Organic and Biomolecular Chemistry, 2019, vol. 17, # 7, p. 1854 - 1861]
[3]Li, Kangying; Alexakis, Alexandre [Angewandte Chemie - International Edition, 2006, vol. 45, # 45, p. 7600 - 7603]
[4]Ogasawara, Masamichi; Okada, Atsushi; Nakajima, Kiyohiko; Takahashi, Tamotsu [Organic Letters, 2009, vol. 11, # 1, p. 177 - 180]
[5]Lujan-Montelongo, Jesus Armando; Fleming, Fraser F. [Organic Syntheses, 2013, vol. 90, p. 229 - 239]

37
[ 917917-78-3 ]
[ 1121-66-0 ]
rac-6-chloro-3-(3-chloro-benzyl)-3-(3-oxo-cycloheptyl)-1,3-dihydro-indol-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In methanol at 100℃; for 0.5h;	87 rac-6-chloro-3-(3-chloro-benzyl)-3-(3-oxo-cycloheptyl)-1,3-dihydro-indol-2-one EXAMPLE 87 rac-6-chloro-3-(3-chloro-benzyl)-3-(3-oxo-cycloheptyl)-1,3-dihydro-indol-2-one A mixture of rac-6-chloro-3-(3-chloro-benzyl)-1,3-dihydro-indol-2-one (0.23 g, 0.90 mmol) (from Example 30b supra), 2-cyclohept-2-enone (0.25 g, 1.80 mmol) (Aldrich), 1,8-diazabicyclo[5.4.0]undec-7-ene (0.68 g, 4.48 mmol) (Fluka AG) in methanol (20 mL) was heated at 100° C. for 0.5 hour. After cooling, the mixture was concentrated, diluted with water, extracted with ethyl acetate. The organic layers were separated, dried over Na2SO4 and concentrated. The residue was purified by chromatography (EtOAc:hexanes=1:2, V/V) to give rac-6-chloro-3-(3-chloro-benzyl)-3-(3-oxo-cycloheptyl)-1,3-dihydro-indol-2-one (Yield 0.31 g, 97%). HRMS(ES+) m/z Calcd for C22H21Cl2NO2+Na [(M+Na)+]: 424.0841. Found: 424.0844.

Reference： [1]Current Patent Assignee: ROCHE HOLDING AG - US2006/293319, 2006, A1 Location in patent: Page/Page column 49

38
[ 1121-66-0 ]
[ 1026994-62-6 ]

Yield	Reaction Conditions	Operation in experiment
82%	With dihydrogen peroxide In 1,4-dioxane at 30℃; for 20h;
95% ee	Stage #1: 2-Cyclohepten-1-one With 4,8-di-tert-butyl-6-hydroxy-12-(2-methoxyphenyl)-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocine 6-oxide; (R)-1-phenyl-2-(piperidin-1-yl)ethan-1-amine In 1,4-dioxane at 20℃; for 0.25h; Sealed tube; Stage #2: With dihydrogen peroxide In 1,4-dioxane; lithium hydroxide monohydrate at 35℃; for 48h; Sealed tube; enantioselective reaction;

Reference： [1]Wang, Xingwang; Reisinger, Corinna M.; List, Benjamin [Journal of the American Chemical Society, 2008, vol. 130, # 19, p. 6070 - 6071]
[2]Scharinger, Fabian; Pálvölgyi, Ádám Márk; Weisz, Melanie; Weil, Matthias; Stanetty, Christian; Schnürch, Michael; Bica-Schröder, Katharina [Angewandte Chemie - International Edition, 2022, vol. 61, # 26][Angew. Chem., 2022, vol. 134, # 26]

39
[ 1121-66-0 ]
[ 1026994-63-7 ]

Yield	Reaction Conditions	Operation in experiment
62%	With dihydrogen peroxide In 1,4-dioxane at 30 - 50℃;
	Stage #1: 2-Cyclohepten-1-one With 9-amino(9-deoxy)epiquinidine di(trifluoroacetic acid) In 1,4-dioxane at 20℃; for 0.5h; Stage #2: With dihydrogen peroxide In 1,4-dioxane; lithium hydroxide monohydrate at 35 - 50℃; enantioselective reaction;
96% ee	Stage #1: 2-Cyclohepten-1-one With 4,8-di-tert-butyl-6-hydroxy-12-(2-methoxyphenyl)-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocine 6-oxide; (S)-1-phenyl-2-(piperidin-1-yl)ethan-1-amine In 1,4-dioxane at 20℃; for 0.25h; Sealed tube; Stage #2: With dihydrogen peroxide In 1,4-dioxane; lithium hydroxide monohydrate at 35℃; for 48h; Sealed tube; enantioselective reaction;

Reference： [1]Wang, Xingwang; Reisinger, Corinna M.; List, Benjamin [Journal of the American Chemical Society, 2008, vol. 130, # 19, p. 6070 - 6071]
[2]Location in patent: experimental part Jiang, Hao; Holub, Nicole; Jørgensen, Karl Anker [Proceedings of the National Academy of Sciences of the United States of America, 2010, vol. 107, # 48, p. 20630 - 20635]
[3]Scharinger, Fabian; Pálvölgyi, Ádám Márk; Weisz, Melanie; Weil, Matthias; Stanetty, Christian; Schnürch, Michael; Bica-Schröder, Katharina [Angewandte Chemie - International Edition, 2022, vol. 61, # 26][Angew. Chem., 2022, vol. 134, # 26]

40
[ 1121-66-0 ]
[ 79722-21-7 ]
[ 1033064-96-8 ]

Yield	Reaction Conditions	Operation in experiment
99%	With potassium hydroxide In toluene at 20℃; for 0.166667h;

Reference： [1]Lee, Jihoon; Kim, Mi-Hyun; Jew, Sang-Sup; Park, Hyeung-Geun; Jeong, Byeong-Seon [Chemical Communications, 2008, # 16, p. 1932 - 1934]

41
[ 1121-66-0 ]
[ 288-36-8 ]
[ 1104001-97-9 ]
[ 1104001-83-3 ]

Reference： [1]Heterocycles,2008,vol. 76,p. 1141 - 1154

42
[ 1121-66-0 ]
[ 312-40-3 ]
[ 501919-44-4 ]
[ 435269-65-1 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: difluorodiphenylsilane With tris(dimethylamino)sulfonium trimethylsilyldifluoride In dichloromethane for 0.0833333h; Inert atmosphere; Stage #2: 2-Cyclohepten-1-one With C₄₁H₄₂BrCuN₂ In dichloromethane at 40℃; for 20h; Inert atmosphere; Stage #3: With hydrogenchloride; water In dichloromethane optical yield given as %ee; enantioselective reaction;

Reference： [1]Location in patent: body text Lee, Kang-Sang; Hoveyda, Amir H. [Journal of Organic Chemistry, 2009, vol. 74, # 12, p. 4455 - 4462]

43
[ 50-00-0 ]
[ 1121-66-0 ]
[ 114908-52-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With dmap; cetyltrimethylammonim bromide In water at 20℃; for 2.8h;	In a typical reaction procedure, a mixture of 11c (110 mg, 1.0 mmol) and aqueous 37% solution 8i (2.0 mmol) was added to an aqueous solution of 4 (at or above CMC; 2 mL). To this mixture, DMAP (12.2 mg, 0.1 mmol) was added and the reaction was stirred at ambient temperature till its completion, monitored by TLC. The crude reaction mixture was diluted with water and extracted with ethylacetate to yield the pure MBH adduct. Spectral data of representative compounds; compound 12j: IR: 3433, 3056, 1653, 1263, 742 cm-1; 1H NMR (CDCl3, 400 MHz): δ 1.80 (m, 4H), 2.47 (q, 2H, J = 8.0 Hz), 2.63 (m, 2H), 2.90 (br s, -OH), 4.23 (s, 2H), 6.77 (t, 1H, J = 8.0 Hz); 13C NMR (100 MHz): δ 21.4, 25.2, 27.9, 43.0, 64.8, 141.7, 144.9, 205.6; ESI-MS, 163.18 [M+Na];
	With 1H-imidazole In tetrahydrofuran; water at 20℃;

Reference： [1]Shairgojray, Bashir Ahmad; Dar, Aijaz Ahmad; Bhat, Bilal Ahmad [Tetrahedron Letters, 2013, vol. 54, # 19, p. 2391 - 2394]
[2]Xu, Junye; Fu, Xiao; Low, Ruijuan; Goh, Yong-Peng; Jiang, Zhiyong; Tan, Choon-Hong [Chemical Communications, 2008, # 43, p. 5526 - 5528]

44
[ 1121-66-0 ]
[ 13361-32-5 ]
[ 1196977-38-4 ]

Yield	Reaction Conditions	Operation in experiment
67%	With potassium carbonate In acetonitrile at 20℃; for 24h;

Reference： [1]Location in patent: experimental part Kim, Se Hee; Kim, Eun Sun; Kim, Taek Hyeon; Kim, Jae Nyoung [Tetrahedron Letters, 2009, vol. 50, # 46, p. 6256 - 6260]

45
[ 496-15-1 ]
[ 1121-66-0 ]
[ 1383687-22-6 ]

Yield	Reaction Conditions	Operation in experiment
96%	With dmap In dichloromethane at 20℃; for 24h;	4.2. General procedure of Lewis acid/base catalyzed Michael addition of indoline with α,β-unsaturated systems General procedure: To a solution of indoline (1.0 mmol) and Michael acceptor (1.0 mmol) in CH2Cl2 (10 mL) was added Lewis acid/base (0.1 mmol). The mixture was stirred until the starting material disappeared (TLC, hexane/ethyl acetate). After evaporation of the solvent, the crude product was dissolved with EtOAc (40 mL) and the organic phase was washed with water (2×20 mL). The EtOAc extract was dried over Na2SO4, filtered, evaporated in vacuo, and the compound was purified by silica gel column chromatography (hexane/ethyl acetate).
	With dmap In acetonitrile at 20℃; regioselective reaction;

Reference： [1]Location in patent: experimental part Kilic, Haydar; Bayindir, Sinan; Erdogan, Esra; Saracoglu, Nurullah [Tetrahedron, 2012, vol. 68, # 27-28, p. 5619 - 5630]
[2]Location in patent: experimental part Bayindir, Sinan; Erdogan, Esra; Kilic, Haydar; Saracoglu, Nurullah [Synlett, 2010, # 10, p. 1455 - 1458]

46
[ 1121-66-0 ]
[ 1119-90-0 ]
(S)-3-n-butylcycloheptanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With 1-[2-((S)-1-hydroxy-3,3-dimethyl-2-butanylamino)-2-oxoethyl]-3-benzylbenzimidazolium chloride; copper(II) bis(trifluoromethanesulfonate) In tetrahydrofuran; hexane at 0 - 20℃; optical yield given as %ee; enantioselective reaction;
99%	With 1-[2-((S)-1-hydroxy-3,3-dimethyl-2-butanylamino)-2-oxoethyl]-3-benzylbenzimidazolium chloride; copper(II) bis(trifluoromethanesulfonate) In tetrahydrofuran at 0 - 20℃; for 3h; optical yield given as %ee; enantioselective reaction;	4.3. General procedure for the Cu(OTf)₂-catalyzed ECA of enone with R₂Zn General procedure: To a solution of azolium salt (0.045 mmol) in THF (9 mL) were added Cu(OTf)2 (0.045 mmol) and enone (1 mmol). After the mixture was cooled to 0 °C, Et2Zn (3 mmol, 1 mol/L in hexanes) was added to the reaction vessel. The color immediately changed from yellow to dark brown. After stirring at room temperature for 3 h, the reaction was quenched with 10% HCl aq. The resulting mixture was extracted with diisopropyl ether and dried over Na2SO4. The product was purified by silica gel column chromatography (hexane/EtOAc). The ee was measured by chiral GLC.

Reference： [1]Location in patent: experimental part Shibata, Naoatsu; Okamoto, Masaki; Yamamoto, Yuko; Sakaguchi, Satoshi [Journal of Organic Chemistry, 2010, vol. 75, # 16, p. 5707 - 5715]
[2]Location in patent: experimental part Yoshimura, Misato; Shibata, Naoatsu; Kawakami, Miaki; Sakaguchi, Satoshi [Tetrahedron, 2012, vol. 68, # 17, p. 3512 - 3518]

47
[ 1121-66-0 ]
[ 25776-12-9 ]
[ 1310421-07-8 ]

Reference： [1]Angewandte Chemie - International Edition,2011,vol. 50,p. 4876 - 4878

48
[ 497-26-7 ]
[ 1121-66-0 ]
[ 1332861-29-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	With (Bu₄N)₂S₂O₈ In 1,2-dichloro-ethane at 70℃; for 1.5h; Inert atmosphere; regioselective reaction;	Typical experimental procedure: A mixture of methyl crotonate (50.1 mg, 0.50 mmol), TBAP (677.0 mg, 1.0 mmol) and 2-methyl-1,3-dioxolane (881.1 mg, 10.0 mmol) in anhyd dichloroethane (2 mL) was heated at 70 °C for 2.5 h under Ar. The reaction mixture was concentrated to give a viscous oil which was diluted with saturated aqueous NaHCO3 (1 mL) and distilled H2O (10 mL). The product was extracted with Et2O (10 mL × 3), and the combined organic layers were dried over anhyd MgSO4, filtered and concentrated. The oily residue was purified by flash chromatography on SiO2 (Et2O/hexane = 1:3) to afford methyl 3-(2-methyl-1,3-dioxolan-2-yl)butanoate (93.0 mg, 99 %).

Reference： [1]Location in patent: experimental part Jung, Jae Chul; Kim, Yong Hae; Lee, Kieseung [Tetrahedron Letters, 2011, vol. 52, # 36, p. 4662 - 4664]

49
[ 1121-66-0 ]
[ 1122410-32-5 ]
[ 75-16-1 ]
(R,R)-benzyl ((2-ethyl-7-oxocycloheptyl)methyl)carbamate [ No CAS ]
(S,S)-benzyl ((2-ethyl-7-oxocycloheptyl)methyl)carbamate [ No CAS ]
benzyl ((2-ethyl-7-oxocycloheptyl)methyl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2-Cyclohepten-1-one With (R,Rp)-1-(2-(diphenylphosphino)ferrocenyl)-1-(2-diphenylphosphinophenyl)-N,N-dimethylmethanamine; copper(l) chloride In dichloromethane at -60℃; for 0.166667h; Inert atmosphere; Stage #2: methylmagnesium bromide In dichloromethane at -60℃; for 2.08333h; Inert atmosphere; Stage #3: benzyl isopropoxymethyl carbamate In dichloromethane at -60 - 20℃; Inert atmosphere; optical yield given as %ee; enantioselective reaction;

Reference： [1]Bilcik, Filip; Drusan, Michal; Marak, Jozef; Sebesta, Radovan [Journal of Organic Chemistry, 2012, vol. 77, # 1, p. 760 - 765]

50
[ 1121-66-0 ]
[ 919089-43-3 ]

Yield	Reaction Conditions	Operation in experiment
73%	With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; potassium hydroxide In 1,4-dioxane; water at 90℃; for 2h; Inert atmosphere; regioselective reaction;	Typical reaction procedure for the synthesis of 2a: General procedure: Two-necked flask (10 mL) equipped with a septum, magnetic stir bar, condenser, and a three-way stopcock connected to nitrogen-balloon system and subjected to evacuated protocol was charged with Rh(I)(cod)2BF4 (9 mg, 0.02 mmol). To this, 2 ml of 1,4-dioxane and water (9:1) was added followed by cyclohexenone (1 mmol). The resulting reaction mixture was stirred for 5 min and KOH solution (2 M, 20 μL, 0.41 mmol) is added. The combined contents were heated to 90 °C for 2 h. Thereafter, the reaction was cooled to ambient temperature and filtered through a plug of Celite and washed with EtOAc (3 × 5 mL). The filtrate was concentrated under reduced pressure to give crude residue which was purified by silica gel column chromatography eluting with hexane/EtOAc (9:1) furnished 2a 174 mg (90%) as dense liquid.

Reference： [1]Kumaraswamy, Gullapalli; Rambabu, Dasa [Tetrahedron Letters, 2012, vol. 53, # 9, p. 1042 - 1044]

51
[ 1121-66-0 ]
[ 25109-28-8 ]
[ 1391920-75-4 ]

Reference： [1]Angewandte Chemie - International Edition,2012,vol. 51,p. 5355 - 5358

52
[ 1121-66-0 ]
[ 936641-27-9 ]
[ 1374988-84-7 ]

Yield	Reaction Conditions	Operation in experiment
83%	With C₅₀H₆₈Cl₂O₄Rh₂; caesium carbonate In 1,4-dioxane; water at 70℃; for 4h; optical yield given as %ee; enantioselective reaction;	4.3. Typical procedure for the rhodium-catalyzed asymmetric 1,4-addition (entry 12 in Table 1) General procedure: To a solution of [RhCl((R)-L3)]2 (5.0 mg, 10 μmol of Rh, 5 mol % Rh), Cs2CO3 (97.7 mg, 0.30 mmol), and (E)-1,2-diphenylethenylboronic acid 1 (89.6 mg, 0.40 mmol) in dioxane (1.0 mL) was added 2-cyclohexenone 2a (19.2 mg, 0.20 mmol) and H2O (50 μL). After stirring at 70 °C for 4 h, the reaction mixture was diluted with Et2O (1.0 mL), and filtered through a pad of silica gel. The plug was washed with Et2O (30 mL) and the combined filtrates were concentrated on a rotary evaporator. The residue was purified by preparative TLC on silica gel with hexane/EtOAc (3/1) to give 3a (54.5 mg, 99% yield). The data for 3a, 3b, 3c, 3d, and 3i have already been reported.7

Reference： [1]Location in patent: experimental part Sasaki, Keigo; Hayashi, Tamio [Tetrahedron Asymmetry, 2012, vol. 23, # 5, p. 373 - 380]

53
[ 1121-66-0 ]
[ 4096-38-2 ]
[ 502-41-0 ]

Yield	Reaction Conditions	Operation in experiment
77%	With sodium tetrahydroborate; calcium(II) trifluoromethanesulfonate In tetrahydrofuran; methanol at 20℃; for 0.5h; Inert atmosphere; regioselective reaction;
	With sodium tetrahydroborate; erbium(III) triflate In 2-methyltetrahydrofuran at 20℃; for 0.0833333h; Green chemistry; Overall yield = > 99 %Chromat.; regioselective reaction;	6 4.2 General procedure for the stereoselective reduction of α,β-unsaturated carbonyl compounds General procedure: To a suspension of α,β-unsaturated carbonyl compound (2.0 mmol) and Er(OTf)3 (0.1 mmol) in 2-MeTHF (3 mL) an equimolar quantity of NaBH4 (2.0 mmol) was added. The reaction mixture was stirred at room temperature and monitored by GC/MS until consumption of starting material. The crude reaction mixture was quenched with H2O (3 mL), the organic phase was dried on dry Na2SO4 and the solvent was evaporated under reduced pressure. The desired product was obtained pure after work-up.

Reference： [1]Forkel, Nina V.; Henderson, David A.; Fuchter, Matthew J. [Green Chemistry, 2012, vol. 14, # 8, p. 2129 - 2132]
[2]Nardi, Monica; Sindona, Giovanni; Costanzo, Paola; Oliverio, Manuela; Procopio, Antonio [Tetrahedron, 2015, vol. 71, # 7, p. 1132 - 1135]

54
[ 2564-83-2 ]
[ 1121-66-0 ]
3-chloro-2-((2,2,6,6-tetramethylpiperidin-1-yl)oxy)cycloheptanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With 2-chloro-1,3,2-benzodioxaborole In dichloromethane at 0℃;

Reference： [1]Li, Yi; Pouliot, Martin; Vogler, Thomas; Renaud, Philippe; Studer, Armido [Organic Letters, 2012, vol. 14, # 17, p. 4474 - 4477]

55
[ 4248-19-5 ]
[ 1121-66-0 ]
[ 1209481-80-0 ]

Yield	Reaction Conditions	Operation in experiment
61%	With bismuth(III) nitrate In dichloromethane at 20℃; for 24h;	134.1 Step 1: Synthesis of tert-butyl N-(3-oxocycloheptyl)carbamate To a solution of cyclohept-2-en-1-one (6.00 g, 54.47 mmol) and tert-butyl carbamate (6.38 g, 54.47 mmol) in dichloromethane (240.0 mL) was added bismuth nitrate (10.76 g, 27.23 mmol) in portions. After stirring at 20 °C for 24 hours, the reaction mixture was diluted with dichloromethane and washed with brine. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. Purification via silica gel column chromatography (ethyl acetate/petroleum ether) afforded the title compound as a light yellow solid. Yield: 9.00 g, 61%.1H NMR (Chloroform-d, 400 MHz) δ 4.58 (s, 1H), 3.91 (s, 1H), 2.78- 2.86 (m, 1H), 2.43-2.65 (m, 3H), 1.91-2.00 (m, 1H), 1.79-1.89 (m, 1H), 1.60-1.77 (m, 4H), 1.43 (s, 9H).
61%	With bismuth(III) nitrate In dichloromethane at 20℃; for 24h;	134.1 Step 1: Synthesis of tert-butyl N-(3-oxocycloheptyl)carbamate To a solution of cyclohept-2-en-1-one (6.00 g, 54.47 mmol) and tert-butyl carbamate (6.38 g, 54.47 mmol) in dichloromethane (240.0 mL) was added bismuth nitrate (10.76 g, 27.23 mmol) in portions. After stirring at 20 °C for 24 hours, the reaction mixture was diluted with dichloromethane and washed with brine. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. Purification via silica gel column chromatography (ethyl acetate/petroleum ether) afforded the title compound as a light yellow solid. Yield: 9.00 g, 61%.1H NMR (Chloroform-d, 400 MHz) δ 4.58 (s, 1H), 3.91 (s, 1H), 2.78- 2.86 (m, 1H), 2.43-2.65 (m, 3H), 1.91-2.00 (m, 1H), 1.79-1.89 (m, 1H), 1.60-1.77 (m, 4H), 1.43 (s, 9H).
55.9%	In dichloromethane at 20℃;	12A.A To a stirring mixture of cyclohept-2- enone (26.96 g, 245.0 mmol) and tert-butyl carbamate (28.7 g, 245 mmol) in DCM (245 mL) was added bismuth nitrate pentahydrate (22.79 g, 47.0 mmol). The resulting mixture was stirred at room temperature overnight. The reaction was diluted reaction with ethyl acetate (500 mL) and water (300 mL) and the biphasic mixture was filtered through a bed of Celite. The bed of Celite was washed well with ethyl acetate and water, and layers of the filtrate separated. The organic layer was concentrated to an oil that was purified by silica gel chromatography (0-40% ethyl acetate in hexanes). Product containing fractions were concentrated to afford the title compound (31.09 g, 137 mmol, 55.9 % yield). 1H NMR (400 MHz, DMSO-d6) δ ppm 6.92 (d, J=7.03 Hz, 1 H), 3.60 (d, J=8.59 Hz, 1 H), 2.55 - 2.69 (m, 1 H), 2.26 - 2.45 (m, 2 H), 1.69 - 1.93- 93 -ATI-2514175vl (m, 3 H), 1.44 - 1.61 (m, 2 H), 1.37 (d, J=5.08 Hz, 11 H). MS (ESI) m z 228.5 [M+H]+.

Reference： [1]Current Patent Assignee: GOSSAMER BIO SERVICES - WO2022/109492, 2022, A1 Location in patent: Page/Page column 454-455
[2]Current Patent Assignee: GOSSAMER BIO SERVICES - WO2022/109492, 2022, A1 Location in patent: Page/Page column 454-455
[3]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2012/145569, 2012, A1 Location in patent: Page/Page column 93; 94

56
[ 1121-66-0 ]
[ 123-11-5 ]
2-[hydroxy-(4-methoxy-phenyl)-methyl]-cyclohept-2-enone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With dmap; 1,5-bis(N-hexadecyl-N,N-dimethylammonium)pentane dibromide In water at 20℃; for 16h;	In a typical reaction procedure, a mixture of 11c (110 mg, 1.0 mmol) and aqueous 37% solution 8i (2.0 mmol) was added to an aqueous solution of 4 (at or above CMC; 2 mL). To this mixture, DMAP (12.2 mg, 0.1 mmol) was added and the reaction was stirred at ambient temperature till its completion, monitored by TLC. The crude reaction mixture was diluted with water and extracted with ethylacetate to yield the pure MBH adduct.

Reference： [1]Shairgojray, Bashir Ahmad; Dar, Aijaz Ahmad; Bhat, Bilal Ahmad [Tetrahedron Letters, 2013, vol. 54, # 19, p. 2391 - 2394]

57
[ 1121-66-0 ]
[ 552-89-6 ]
[ 1429622-79-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	With dmap; cetyltrimethylammonim bromide In water at 20℃; for 7.5h;	In a typical reaction procedure, a mixture of 11c (110 mg, 1.0 mmol) and aqueous 37% solution 8i (2.0 mmol) was added to an aqueous solution of 4 (at or above CMC; 2 mL). To this mixture, DMAP (12.2 mg, 0.1 mmol) was added and the reaction was stirred at ambient temperature till its completion, monitored by TLC. The crude reaction mixture was diluted with water and extracted with ethylacetate to yield the pure MBH adduct.

Reference： [1]Shairgojray, Bashir Ahmad; Dar, Aijaz Ahmad; Bhat, Bilal Ahmad [Tetrahedron Letters, 2013, vol. 54, # 19, p. 2391 - 2394]

58
[ 1121-66-0 ]
[ 128637-49-0 ]
[ 1434079-34-1 ]

Yield	Reaction Conditions	Operation in experiment
97%	With toluene-4-sulfonic acid In ethanol at 20℃; for 1h;	4.3 Typical procedure for the preparation of Michael addition products (4a-d) General procedure: To a stirred solution of ethyl 4-ethoxyazulene-1-carboxylate 1 (1 mmol, 0.244 g) in EtOH (4 mL) were added methyl vinyl ketone or cyclopentenone or cyclohexenone or cycloheptenone (1.2 mmol), and p-TSA (1.1 mmol, 0.189 g) at room temperature, and the reaction continued for 40 min (4a-c) to 1 h (4d). Aqueous KOH solution was added slowly to neutralize the reaction and the reaction mixture was extracted with EtOAc; the combined organic layers were dried over anhydrous MgSO4, filtered, and stripped off solvent to give mixture of crude products were isolated by silica gel column chromatography.

Reference： [1]Devendar, Badugu; Wu, Chi-Phi; Chen, Chi-Yuan; Chen, Hung-Chang; Chang, Chung-Hao; Ku, Chien-Kuo; Tsai, Cheng-Yin; Ku, Chieh-Yuan [Tetrahedron, 2013, vol. 69, # 24, p. 4953 - 4963]

59
[ 1021359-62-5 ]
[ 1121-66-0 ]
2-{3-hydroxy-5-[hydroxy-(7-oxo-cyclohept-1-enyl)-methyl]-1-methyl-2-oxo-2,3-dihydro-1H-indol-3-yl}-acrylic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With 1,4-diaza-bicyclo[2.2.2]octane In neat (no solvent) at 20℃; for 20h;	2.1 General procedure for the synthesis of bis-MBH adducts (3a-m) General procedure: A mixture of mMBH adducts of 5-formyl-N-alkylisatin 1a-g (100 mg), activated alkenes 2a-g (1.5 equiv.) and DABCO (20 mol%) was stirred under neat conditionat for 8-32 h. After completion of the reaction(monitored by TLC), the reaction mixture was diluted with ethyl acetate. The organic layer was washed successively with 0.2N HCl, water and then brine solution.The organic layer was separated, dried over Na2SO4 and then concentrated in vacuo. The crude product was obtained and purified by silica gel column chromatography using EtOAc: hexane (40:60) as eluent.The desired bis-MBH adducts of oxindole (3a-m) was obtained in moderate to excellent yield (45-94%).

Reference： [1]Selvakumar, Kodirajan; Prasath Lingam, Kandapalam Arun; Luxmi Varma, Rama Varma; Shanmugavelan, Poovan [Journal of Chemical Sciences, 2015, vol. 127, # 8, p. 1417 - 1426]

60
[ 19063-55-9 ]
[ 1121-66-0 ]
[ 42201-84-3 ]
ethyl 2-(6-bromo-2-oxo-3-(3-oxocycloheptyl)chroman-4-yl)acetate [ No CAS ]
ethyl 2-(6-bromo-2-oxo-3-(3-oxocycloheptyl)chroman-4-yl)acetate [ No CAS ]

Reference： [1]Chemical Communications,2016,vol. 52,p. 3280 - 3283

61
[ 1121-66-0 ]
C₁₄H₁₆O₃Te [ No CAS ]
[ 1326319-36-1 ]

Yield	Reaction Conditions	Operation in experiment
78%	With triethyl borane; oxygen In hexane; dichloromethane at 0℃; for 0.25h;	26 4.2. General procedure A: synthesis of compound 7a from O,Te-acetal 2 [CAS: 1326319-34-9] General procedure: Et3B (1.03 M in hexane, 0.37 mL, 0.38 mmol) was added to a solution of O,Te-acetal 29a (46.1 mg, 0.128 mmol) and cyclopentenone 3a (32 mL, 0.38 mmol) in CH2Cl2 (1.3 mL) at 0 °C. The reaction mixture was stirred for 15 min at 0 °C, and was then directly subjected to flash column chromatography on silica gel (10 g, hexane/EtOAc 1/1) to afford 7a (26.9 mg, 0.113 mmol) in 88% yield. The analytical data of 7a were identical to those reported previously.2a

Reference： [1]Kamimura, Daigo; Nagatomo, Masanori; Urabe, Daisuke; Inoue, Masayuki [Tetrahedron, 2016, vol. 72, # 48, p. 7839 - 7848]

62
[ 1121-66-0 ]
[ 1633-44-9 ]
C₁₃H₁₄N₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
19%	With bis(pinacolato)diborane In tert-butyl methyl ether at 70℃; for 24h; Inert atmosphere; Sealed tube;

Reference： [1]Wang, Guoqiang; Cao, Jia; Gao, Liuzhou; Chen, Wenxin; Huang, Wenhao; Cheng, Xu; Li, Shuhua [Journal of the American Chemical Society, 2017, vol. 139, # 10, p. 3904 - 3910]

63
[ 1121-66-0 ]
[ 68325-15-5 ]
C₁₂H₁₄ClNO [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 3904 - 3910

64
[ 113770-88-0 ]
[ 1121-66-0 ]
C₁₂H₁₄FNO [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 3904 - 3910

65
[ 7584-05-6 ]
[ 1121-66-0 ]
C₁₃H₁₇NO [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 3904 - 3910

66
[ 1121-66-0 ]
[ 13958-98-0 ]
C₁₂H₁₄BrNO [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 3904 - 3910

67
[ 1121-66-0 ]
[ 1826-67-1 ]
[ 28399-94-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	Stage #1: vinyl magnesium bromide With N,N,N,N,N,N-hexamethylphosphoric triamide; copper(I) bromide dimethylsulfide complex In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: 2-Cyclohepten-1-one With chloro-trimethyl-silane In tetrahydrofuran at -78℃; for 2.5h; Inert atmosphere;	12.A Step A. 3-Vinylcycloheptan-1-one Step A. 3-Vinylcycloheptan-1-one Vinylmagnesium bromide (1M in THF) (18.2 mL, 18.2 mmol) and HMPA (6.31 mL, 36.3 mmol) were separately added dropwise to a suspension of CuBrMe2S (281 mg 1.36 mmol) in dry THF (70 mL) at -78° C. under argon over 10 min. After stirring at -78° C. for 15 min a solution of cyclohept-2-en-1-one (1 g 9.1 mmol) and TMSCl (5.77 ml, 45.5 mmol) in dry THF (20 mL) was added dropwise over 30 min. The reaction mixture was stirred at -78° C. for 2 h. Then the mixture was quenched with saturated NH4Cl (130 mL) and washed with AcOEt (3100 ml). The organic layers were dried over MgSO4 and concentrated. The crude product was purified by flash chromatography on silica gel (DCM) to give 3-vinylcycloheptan-1-one (1.3 g 100%) as a yellow liquid. 1H NMR (700 MHz, chloroform-d) δ 5.81 (ddd, J=17.2, 10.4, 6.8 Hz, 1H), 5.06-4.94 (m, 2H), 2.58-2.56 (m, 2H), 2.54-2.50 (m, 2H), 2.44-2.38 (m, 1H), 2.01-1.86 (m, 3H), 1.69-1.58 (m, 1H), 1.51-1.41 (m, 2H).
44%	Stage #1: 2-Cyclohepten-1-one With copper(I) bromide dimethylsulfide complex In tetrahydrofuran at 20℃; for 0.25h; Inert atmosphere; Stage #2: vinyl magnesium bromide In tetrahydrofuran at -40℃; for 2h; Inert atmosphere;	Intermediate 1A. 3-vinylcycloheptan-l-one To a solution of cyclohept-2-enone (1.45 g, 13.16 mmol) in THF (65.8 ml) was added CuBr*SMe2 complex (0.27 g, 1.3 mmol) under Ar at RT and the reaction was stirred at RT for 15 min, then was cooled to -40°C. Vinylmagnesium bromide (19.7 mL of a 1M solution in THF; 19.7 mmol) was added over 1 h via syringe pump at -40°C. The reaction mixture was stirred at -40°C for 1 h, then was quenched with satd aq. NH4Cl at -40°C. The mixture was allowed to warm to RT and extracted with EtOAc (50 mL X 2). The combined organic extracts were dried (Na2S04) and concentrated in vacuo. The crude product was chromatographed (80 g S1O2 ISCO column; continuous gradient from 0% to 50% EtOAc in hexanes over 20 min) to give the title compound (800 mg, 5.79 mmol, 44.0 % yield). NMR (400 MHz, CDCh) d 5.89 - 5.74 (m, 1H), 5.10 - 4.94 (m, 2H), 2.61 - 2.49 (m, 4H), 2.46 - 2.35 (m, 1H), 2.03 - 1.86 (m, 3H), 1.72 - 1.60 (m, 1H), 1.52 - 1.40 (m, 2H).

Reference： [1]Current Patent Assignee: ONCOARENDI THERAPEUTICS SA - US2017/319536, 2017, A1 Location in patent: Paragraph 0670; 0671; 0672
[2]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2020/60916, 2020, A1 Location in patent: Page/Page column 82

68
[ 1121-66-0 ]
[ 627-30-5 ]
3-(3-chloropropoxy)cycloheptan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With bismuth(III) chloride at 20℃; for 24h;	General procedure for the hydroalkoxylation of cyclic enones General procedure: Cyclic enones (1s-t, 1.0 mmol, 1.0 equiv.), alcohol 3 (6 equiv.), and BiCl3 (0.0631 g, 0.20mmol, 20 mol%) were stirred in CH3CN (1 mL) at room temperature for 24 h. Upon completion of the reaction (as indicated by TLC), the reaction mixture was directly concentrated in vacuo. The crude residue obtained was purified by silica gel column chromatography using ethyl acetate and petroleum ether as eluant to afford the pure β-alkoxyl ketone 4m-q.
83%	With chromium(III) chloride hexahydrate In acetonitrile at 20℃; for 24h;
51%	With indium(III) triflate In acetonitrile at 20℃; for 24h;

Reference： [1]Wu, Zhen; Feng, Xue-Xin; Wang, Qing-Dong; Yun, Jin-Jin; Rao, Weidong; Yang, Jin-Ming; Shen, Zhi-Liang [Chinese Chemical Letters, 2020, vol. 31, # 5, p. 1297 - 1300]
[2]Yun, Jin-Jin; Liu, Xuan-Yu; Deng, Wei; Chu, Xue-Qiang; Shen, Zhi-Liang; Loh, Teck-Peng [Journal of Organic Chemistry, 2018, vol. 83, # 18, p. 10898 - 10907]
[3]Yun, Jin-Jin; Zhi, Man-Ling; Shi, Wen-Xiao; Chu, Xue-Qiang; Shen, Zhi-Liang; Loh, Teck-Peng [Advanced Synthesis and Catalysis, 2018, vol. 360, # 14, p. 2632 - 2637]

69
[ 1121-66-0 ]
[ 1066-54-2 ]
1-((trimethylsilyl)ethynyl)cyclohept-2-en-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	Stage #1: trimethylsilylacetylene With n-butyllithium In tetrahydrofuran; hexane at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: 2-Cyclohepten-1-one In tetrahydrofuran; hexane at 0 - 20℃; for 3h; Inert atmosphere;
79%	Stage #1: trimethylsilylacetylene With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 0.166667h; Stage #2: 2-Cyclohepten-1-one In tetrahydrofuran; hexane at 0℃; for 0.5h;	1-((Trimethylsilyl)ethynyl)cyclohex-2-en-1-ol: (±)-S1b General procedure: To a stirred solution of trimethylsilylacetylene (14.4 mL, 102 mmol) in THF (60 mL) at 0 °C was dropwiseadded n-BuLi (2.7 M in n-hexane, 30 mL, 81 mmol). After 10 min of stirring at the same temperature, 2-cyclohexenone (5a) (6.0 mL, 62 mmol) was added, and the stirring was continued for another 30 min. Sat.NH4Cl was added to quench the reaction, and the mixture was transferred to a separatory funnel. It wasextracted with Et2O. The organic combined phases were separated, dried over MgSO4, and filtered. Thesolvent was removed under reduced pressure to afford an oil residue, which was purified by columnchromatography (EtOAc/n-hexane 1:5) to give S1b (10.7 g, 89% yield) as a colorless solid.

Reference： [1]Hsu, Day-Shin; Cheng, Chiao-Yun [Journal of Organic Chemistry, 2019, vol. 84, # 17, p. 10832 - 10842]
[2]Tsuchimochi, Izuru; Hori, Shuhei; Takeuchi, Yasuo; Egi, Masahiro; Satoh, Tomo-O; Kanomata, Kyohei; Ikawa, Takashi; Akai, Shuji [Synlett, 2021, vol. 32, # 8, p. 822 - 828]

70
[ 1121-66-0 ]
[ 1666-13-3 ]
[ 1292308-84-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: diphenyl diselenide With hydrogenchloride; zinc In ethyl acetate at 20℃; for 0.333333h; Sealed tube; Stage #2: 2-Cyclohepten-1-one In ethyl acetate at 20℃; for 2h; Sealed tube;	General Procedure for the Se-Michael-Type Addition General procedure: Diselenides (1, 32, and 33) (0.16 mmol) were introduced to a biphasic system composed of EtOAc(2 mL) and HCl (10% v/v, 2 mL). Then, 1.6 mmol (10 equiv.) of zinc powder (or turnings) were added.The vial was closed and the mixture was vigorously stirred (approx. 800 rpm) at room temperatureuntil the discoloration of the organic layer (approx. 20 min). After that, zinc was removed and theolefin (0.32 mmol) was added to the liquid. The reaction was stirred at room temperature for anadditional 2 h. The ethyl acetate was separated and the resultant aqueous phase extracted with EtOAc(3 2 mL). The organic layers were combined, washed with brine, dried over Na2SO4, filtered, and thesolvent was removed under reduced pressure.

Reference： [1]Evans, Paul; Lenardão, Eder João; Monti, Bonifacio; Nacca, Francesca Giulia; Santi, Claudio [Molecules, 2020, vol. 25, # 9]

71
[ 1121-66-0 ]
[ 69555-14-2 ]
ethyl (2S)-2-(benzhydrylideneamino)-2-[(1S)-3-oxocycloheptyl]acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With cesiumhydroxide monohydrate; Cinchonidin In dichloromethane at -78℃; for 2.16667h;	37 Preparation 37 Ethyl (2S)-2-(benzhydrylideneamino)-2-[(lS)-3-oxocycloheptyl]acetate A solution of cyclohept-2-en-l-one (1.0 g, 9.1 mmol) in DCM (10 mL) was added dropwise over ca. 10 min to a mixture of ethyl 2-(benzhydrylideneamino)acetate (0.8 g, 3.0 mmol), cinchonidine alkaloid (0.2 g, 0.7 mmol), caesium hydroxide monohydrate (3.0 g, 17.9 mmol) in DCM at -78°C. After being stirred for 2 hours at the same temperature, the solution was allowed to warm to room temperature upon which the solution turned from yellow to dark brown. TBME (100 mL) and water (50 mL) were added. The organic phase was washed with water (50 mL), dried over MgSCU, filtered and concentrated in vacuo. The crude product was purified by flash chromatography (silica gel, eluting with heptane/ethyl acetate 2: 1) to give the title compound as an oil (1.02 g, 90%). LCMS (ES) (Method 3) : m/z 378.5 [M + H]+, RT = 0.92 min.

Reference： [1]Current Patent Assignee: LEO FONDET - WO2020/127685, 2020, A1 Location in patent: Page/Page column 51-52

72
[ 1121-66-0 ]
[ 103587-51-5 ]
(E)-cyclohept-2-en-1-one O-(tert-butyldiphenylsilyl)oxime [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
32%	In dichloromethane at 20℃; for 24h;	(E)-Cyclohept-2-en-1-one O-(tert-Butyldiphenylsilyl)oxime(3c) To a stirred solution of O-(tert-butyldiphenylsilyl)hydroxylamine33) (0.804 g, 2.96 mmol) in CH2Cl2 (40 mL) wasadded dropwise cyclohept-2-en-1-one (0.330 mL, 2.96 mmol) atroom temperature. The mixture was stirred at the same temperaturefor 24 h, then washed with H2O, dried (Na2SO4), andconcentrated under reduced pressure. The residue was purifiedby column chromatography on silica gel (hexane-CHCl3,2/1) to give 3c (0.237 g, 32%) as crystals. mp 50.5-51.5 °C;IR (NaCl) 2933, 1427 cm-1; 1H-NMR (400 MHz, CDCl3) δ:7.74-7.67 (4H, m), 7.39-7.26 (6H, m), 6.12 (1H, dt, J = 12.4,2.0 Hz), 5.92 (1H, dt, J = 12.4, 4.8 Hz), 2.96-2.89 (2H, m),2.35-2.27 (2H, m), 1.81-1.69 (4H, m), 1.10 (9H, s); 13C-NMR(100 MHz, CDCl3) δ: 165.2, 136.0, 135.4, 133.9, 129.5, 127.5,126.8, 30.8, 28.3, 27.1, 26.9, 23.7, 19.5; HRMS (ESI) m/z Calcdfor C23H30NOSi [M + H]+ 364.2097, Found 364.2082.

Reference： [1]Furugoori, Miyu; Yoshida, Kiwamu; Hashimoto, Yoshimitsu; Morita, Nobuyoshi; Tanaka, Kosaku; Tamura, Osamu [Chemical and Pharmaceutical Bulletin, 2021, vol. 69, # 10, p. 1010 - 1016]

73
[ 1121-66-0 ]
[ 103587-51-5 ]
(E)-8-oxabicyclo[5.1.0]octan-2-one O-(tert-butyldiphenylsilyl)oxime [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: dichloromethane / 24 h / 20 °C 2: sodium hydrogencarbonate; Oxone / acetone; water / 5.5 h / 20 °C

Reference： [1]Furugoori, Miyu; Yoshida, Kiwamu; Hashimoto, Yoshimitsu; Morita, Nobuyoshi; Tanaka, Kosaku; Tamura, Osamu [Chemical and Pharmaceutical Bulletin, 2021, vol. 69, # 10, p. 1010 - 1016]

74
[ 1121-66-0 ]
[ 75-24-1 ]
(R)-3-methylcycloheptanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: tris(methyl)aluminum With copper(I) thiophene-2-carboxylate; (3,5-dioxa-4-phospha-cyclohepta[2,1-<i>a</i>;3,4-<i>a</i>']dinaphthalen-4-yl)-bis-(1-phenyl-ethyl)-amine In diethyl ether at -30℃; for 2h; Inert atmosphere; Stage #2: 2-Cyclohepten-1-one In diethyl ether at -30℃; for 7h; Inert atmosphere;	2 Synthesis of (R)-3-methylcycloheptanone (4) Under argon protection, Cu(TC) (28.6 mg, 0.15 mmol), ligand L1 (307.8 mg, 0.6 mmol) and ultra-dry Et2O (10 mL) were added to a 100 mL Shrek flask, and the reaction was stirred for 1 h.Cool to -30°C and add trimethylaluminum (18 mL, 1M in ether, 18 mmol) dropwise. The reaction was carried out at -30 °C for 1 h, then 2-cyclohepten-1-one (3) (1.100 g, 10 mmol) was added dropwise within 1 h, and the reaction was carried out at -30 °C for 6 h to stop the reaction. The reaction was quenched with ice (5.00 g) and the layers were separated. The aqueous phase was extracted with Et2O (3 x 30 mL) and the organic phases were combined. The organic phase was dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. Finally, it was purified by silica gel column chromatography (petroleum ether:diethyl ether 30:1) to obtain (R)-3-methylcycloheptanone (4) as a colorless oil (1.00 g, yield 85%, optical purity 90%) .

Reference： [1]Current Patent Assignee: CHINA AGRICULTURAL UNIVERSITY - CN113773180, 2021, A Location in patent: Paragraph 0008; 0025-0029

75
[ 182344-29-2 ]
[ 1121-66-0 ]
3-(4'-ethoxybiphenyl-4-yl)cycloheptanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
15%	With 4-dimethylaminopyridine; 10-(3,5-dimethoxyphenyl)-9-mesityl-1,3,6,8-tetramethoxyacridin-10-ium tetrafluoroborate In methanol; propan-2-one for 16h; Sealed tube; Inert atmosphere; Irradiation; Green chemistry;	General procedure for Giese reaction in batch General procedure: An oven dried 5-mL microwave tube equipped with a magnetic stirring bar was charged with [4-(4- ethoxyphenyl)phenyl]boronic acid 1a (40 mg, 0.165 mmol), photoredox catalyst (Mes-Acr; 2.6 mg, 0.004 mmol), DMAP (5.0 mg, 0.041 mmol). The vial was sealed with a septum and 3 cycles vacuum/Argon were performed. A 1:1 acetone/MeOH solvent mixture (purged with argon for 15 minutes) (2 mL), and methylviny ketone 2a (46 mg, 0.660 mmol) were added. The tube was irradiated with Penn PhD Photoreactor M2 (450 nm) for 1 h. The reaction, assayed by HPLC/MS, was concentrated in vacuo, reconstituted in DCM, and purified through flash chromatography (AcOEt/Hexane: 0% for 4 CV then to 90% in 12 CV). 4-[4-(4-ethoxyphenyl)phenyl]butan-2-one 3aa was isolated as white solid (25 mg, y: 56 %).

Reference： [1]Caldarelli, Marina; Laze, Loris; Piazza, Lavinia; Caputo, Giulia; De Amici, Marco; Papeo, Gianluca [Tetrahedron Letters, 2022, vol. 103]

76
[ 1121-66-0 ]
[ 108-98-5 ]
cycloheptane-1,1,3-triyltris(phenylsulfane) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	With lithium perchlorate In diethyl ether; 1,2-dichloro-ethane at 20℃; for 4h; Electrochemical reaction; Green chemistry; chemoselective reaction;	General procedure for Table 2 and Table 3: General procedure: An undivided cellequipped with a graphite anode and a graphite cathode connectedin electrosyn 2.0 instrument was used. Cyclic enones (1.0 mmol),thiols (3.5 mmol) and LiClO4 (50 mol %) were charged in DCE:Diethyl ether (3:2; 5 mL) solvent in a specific electrosyn 2.0 vial.The reaction mixture was stirred and electrolyzed at a constant current of 10 mA at room temperature for a specific time interval.After the completion of the reaction, the reaction mixture wasdiluted with water (20 mL) and extracted with ethyl acetate (3x20mL). The combined organic layer was washed with brine solution(20 mL) and dried over Na2SO4. The combined filtrate wasconcentrated under reduced pressure to get crude compoundwhich was further purified by column chromatography (silica-gel100-200 mesh) using ethyl acetate/hexane as an eluent to affordthe corresponding compounds 3 and 4.

Reference： [1]Yadav, Lalit; Maneesha, Ms.; Dabaria, Kamlesh Kumar; Jat, Pooja Kumari; Gurjar, Asha; Badsara, Satpal Singh [Synthesis, 2022]

77
[ 1121-66-0 ]
[ 100-53-8 ]
cycloheptane-1,1,3-triyltris(benzylsulfane) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With lithium perchlorate In diethyl ether; 1,2-dichloro-ethane at 20℃; for 4h; Electrochemical reaction; Green chemistry; chemoselective reaction;	General procedure for Table 2 and Table 3: General procedure: An undivided cellequipped with a graphite anode and a graphite cathode connectedin electrosyn 2.0 instrument was used. Cyclic enones (1.0 mmol),thiols (3.5 mmol) and LiClO4 (50 mol %) were charged in DCE:Diethyl ether (3:2; 5 mL) solvent in a specific electrosyn 2.0 vial.The reaction mixture was stirred and electrolyzed at a constant current of 10 mA at room temperature for a specific time interval.After the completion of the reaction, the reaction mixture wasdiluted with water (20 mL) and extracted with ethyl acetate (3x20mL). The combined organic layer was washed with brine solution(20 mL) and dried over Na2SO4. The combined filtrate wasconcentrated under reduced pressure to get crude compoundwhich was further purified by column chromatography (silica-gel100-200 mesh) using ethyl acetate/hexane as an eluent to affordthe corresponding compounds 3 and 4.

Reference： [1]Yadav, Lalit; Maneesha, Ms.; Dabaria, Kamlesh Kumar; Jat, Pooja Kumari; Gurjar, Asha; Badsara, Satpal Singh [Synthesis, 2022]

78
[ 111-31-9 ]
[ 1121-66-0 ]
cycloheptane-1,1,3-triyltris(n-hexylsulfane) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With lithium perchlorate In diethyl ether; 1,2-dichloro-ethane at 20℃; for 4h; Electrochemical reaction; Green chemistry; chemoselective reaction;	General procedure for Table 2 and Table 3: General procedure: An undivided cellequipped with a graphite anode and a graphite cathode connectedin electrosyn 2.0 instrument was used. Cyclic enones (1.0 mmol),thiols (3.5 mmol) and LiClO4 (50 mol %) were charged in DCE:Diethyl ether (3:2; 5 mL) solvent in a specific electrosyn 2.0 vial.The reaction mixture was stirred and electrolyzed at a constant current of 10 mA at room temperature for a specific time interval.After the completion of the reaction, the reaction mixture wasdiluted with water (20 mL) and extracted with ethyl acetate (3x20mL). The combined organic layer was washed with brine solution(20 mL) and dried over Na2SO4. The combined filtrate wasconcentrated under reduced pressure to get crude compoundwhich was further purified by column chromatography (silica-gel100-200 mesh) using ethyl acetate/hexane as an eluent to affordthe corresponding compounds 3 and 4.

Reference： [1]Yadav, Lalit; Maneesha, Ms.; Dabaria, Kamlesh Kumar; Jat, Pooja Kumari; Gurjar, Asha; Badsara, Satpal Singh [Synthesis, 2022]

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CAS No. :	1121-66-0	MDL No. :	MFCD00004157
Formula :	C₇H₁₀O	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	WZCRDVTWUYLPTR-UHFFFAOYSA-N
M.W :	110.15	Pubchem ID :	70723
Synonyms :

Num. heavy atoms :	8
Num. arom. heavy atoms :	0
Fraction Csp3 :	0.57
Num. rotatable bonds :	0
Num. H-bond acceptors :	1.0
Num. H-bond donors :	0.0
Molar Refractivity :	33.38
TPSA :	17.07 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.95 cm/s

Log Po/w (iLOGP) :	1.71
Log Po/w (XLOGP3) :	1.44
Log Po/w (WLOGP) :	1.69
Log Po/w (MLOGP) :	1.24
Log Po/w (SILICOS-IT) :	2.03
Consensus Log Po/w :	1.62

[ CAS No. 1121-66-0 ] {[proInfo.proName]}

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[ 1121-66-0 ]

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

Log S (ESOL) :	-1.43
Solubility :	4.09 mg/ml ; 0.0371 mol/l
Class :	Very soluble
Log S (Ali) :	-1.4
Solubility :	4.35 mg/ml ; 0.0394 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-1.18
Solubility :	7.21 mg/ml ; 0.0655 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	2.45

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P280	UN#:	N/A
Hazard Statements:	H227-H302	Packing Group:	N/A
GHS Pictogram:

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P378
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P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
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P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
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P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
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P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
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[ CAS No. 1121-66-0 ] {[proInfo.proName]}

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[ 1121-66-0 ]