16_page_(R)-2-Phenylcyclohexanone [C12H14O] [CAS 34281-93-1; InChIKey DRLVMOAWNVOSPE-LLVKDONJSA-N; R

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Rx-ID: 8613824 View in Reaxys 1/46 Yield

Conditions & References With cellulose tris(3,5-dichlorophenylcarbamate), enantioseparation of racemate Chankvetadze, Bezhan; Yamamoto, Chiyo; Okamoto, Yoshio; Chemistry Letters; nb. 4; (2000); p. 352 - 353 View in Reaxys With DCCD-HPS packed column, nickel(II) perchlorate in hydrogenchloride, acetonitrile, pH= 8.6 Gong, Yinhan; Lee, Hian Kee; Analytical Chemistry; vol. 75; nb. 6; (2003); p. 1348 - 1354 View in Reaxys Stage 1: With chloro-trimethyl-silane, triethylamine in N,N-dimethyl-formamide, Time= 90h, T= 130 °C , enolization; silylation Stage 2: With (R)-BINOL-SnCl4 in dichloromethane, toluene, Time= 1h, T= -78 °C , enantioselective protonation, Further stages. Title compound not separated from byproducts.

Nakamura, Shingo; Kaneeda, Masanobu; Ishihara, Kazuaki; Yamamoto, Hisashi; Journal of the American Chemical Society; vol. 122; nb. 34; (2000); p. 8120 - 8130 View in Reaxys Stage 1: With t-Bu2SiCl, triethylamine in N,N-dimethyl-formamide, Time= 90h, T= 130 °C , enolization; silylation Stage 2: With (R)-BINOL-SnCl4 in dichloromethane, toluene, Time= 1h, T= -78 °C , enantioselective protonation, Further stages. Title compound not separated from byproducts.

Nakamura, Shingo; Kaneeda, Masanobu; Ishihara, Kazuaki; Yamamoto, Hisashi; Journal of the American Chemical Society; vol. 122; nb. 34; (2000); p. 8120 - 8130 View in Reaxys Stage 1: With t-Bu2SiCl, triethylamine in N,N-dimethyl-formamide, Time= 90h, T= 130 °C , enolization; silylation Stage 2: With (S)-BINOL-SnCl4 in dichloromethane, toluene, Time= 1h, T= -78 °C , enantioselective protonation, Further stages. Title compound not separated from byproducts.

Nakamura, Shingo; Kaneeda, Masanobu; Ishihara, Kazuaki; Yamamoto, Hisashi; Journal of the American Chemical Society; vol. 122; nb. 34; (2000); p. 8120 - 8130 View in Reaxys Resolution of racemate Ema, Tadashi; Tanida, Daisuke; Sugita, Kyoko; Sakai, Takashi; Miyazawa, Ken-Ichiro; Ohnishi, Atsushi; Organic Letters; vol. 10; nb. 12; (2008); p. 2365 - 2368 View in Reaxys 5; 4 :The separating agents prepared in Examples 1 and 2 were used as fillers, and filled in stainless columns each having a length of 25 cm and an inner diameter of 2 mm by a slurry filling method to make columns for enantiomeric isomers. Using those columns, optical resolution of enantiomeric compounds shown in Table 3 was performed by liquid chromatography. Analytical conditions are the mobile phase: hexane (H)/chloroform (C)/2-propanol (1) = 90/10/1, a flow rate: 0.1 or 0.2 ml/min, temperature: 25°C, and detection at 254 nm. The separation coefficient (α) in the table was determined by the following formula.Separation coefficient (α) = k2'/k1' : In the formula, k1' = ((t1-t0)/t0) and k2' = ( (t2-t0) /t0) . Those t1 and t2 denote elution times of respective enantiomeric isomers, and t0 denotes an elution time of tri-tert-butylbenzene. Table 1 shows the results when the mobile phase was hexane (H)/chloroform (C)/2-propanol (I) = 90/10/1.; Comparative Example 4 The optical resolution of various enantiomeric compounds was performed using the separating agents prepared in Comparative Examples 1 to 3 by the same method as that in Example 3. Table 1 shows the results. [Table 1] H/C/I=90/10/1 FillerEx. 1Ex. 2Com. Ex. 1Com. Ex. 2Com. Ex. 3Silica gelMA-SiM-SiA-SiMA-SiA-SiPolysaccharide derivative6-CMDMPC6-CMDMPC6-CMDMPC6-CVDMPC6CVDMPCAddition amount of styrene (percent)101010--Immobilization rate (percent)9080997050Enantiomeric compound 11.861.581.681.631.44Enantiomeric compound 21.601.951.01.41.62Enantiomeric compound 31.231.361.21.251.28Enantiomeric compound 41.211.231.21.151.16Enantiomeric compound

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51.371.311.361.31.28Enantiomeric compound 62.523.152.52.412.45Enantiomeric compound 71.01.01.01.01.0Enantiomeric compound 81.201.271.121.211.26Enantiomeric compound 92.042.241.81.911.56Mean of α values1.561.681.431.471.45 in hexane, chloroform, isopropyl alcohol, T= 25 °C , Resolution of racemate, Purification / work up Patent; Daicel Chemical Industries, Ltd.; EP1498404; (2005); (A1) English View in Reaxys 6 :The optical resolution of the enantiomeric compounds shown in Table 3 was performed by the same method as that in Example 5, except that the separating agents prepared in Examples 1 to 4 were used as fillers, the mobile phase was changed to hexane (H)/2-propanol = 90/10, and the flow rate was changed to 0.1 ml/min. Table 2 shows the results. in hexane, isopropyl alcohol, Resolution of racemate, Purification / work up Patent; Daicel Chemical Industries, Ltd.; EP1498404; (2005); (A1) English View in Reaxys 1.2.6 :In a nitrogen atmosphere, 20 ml of pyridine or dimethylsulfoxide was added to 1 g of a polysaccharide (cellulose or amylose), and each of the corresponding isocyanates (1) to (3) and (6) was added thereto in an amount of 1.5 equivalents to that of hydroxyl groups of the polysaccharide, and stirred under heating to thereby obtain each of polysaccharide benzoyl carbamate derivatives (7) to (13) shown in Table 1. In a nitrogen atmosphere, 20 ml of pyridine or dimethylsulfoxide was added to 1 g of a polysaccharide (cellulose or amylose), and each of the corresponding isocyanates (1) to (3) and (6) was added thereto in an amount of 1.5 equivalents to that of hydroxyl groups of the polysaccharide, and stirred under heating to thereby obtain each of polysaccharide benzoyl carbamate derivatives (7) to (13) shown in Table 1. (b) Surface Treatment of Silica GelPorous silica gel (particle size of 7 μm) was reacted with 3-aminopropyl triethoxysilane for aminopropylsilane (APS) treatment.(c) Preparation of Filler for Liquid Chromatography0.225 g of each of the polysaccharide benzoyl carbamate derivatives (7) to (13) obtained in the above section (a) was dissolved in tetrahydrofuran (THF) or dimethylsulfoxide (DMSO), and 0.9 g of silica gel obtained in the above section (b) was evenly coated with the resulting solution. Then, the solvent was distilled off under reduced pressure, to thereby obtain a filler for enantiomeric isomers having the target polysaccharide derivative carried on silica gel.(d) Preparation of Column for Liquid ChromatographyThe filler obtained in the above section (c) was pressed and filled into a stainless column of 0.2 cmΦ.x.25 cmL through a slurry filling method, to thereby prepare an enantiomeric isomer separation column. The enantiomeric isomer separation columns prepared in Examples were each evaluated for asymmetry identifying power (retention factor k' value and separation factor α value) by using the following ten compounds by means of liquid chromatography. Table 2 shows the results.(Analysis Conditions) Mobile phase: hexane/2-propanol=90/10 (v/v)Flow rate: 0.1 ml/minDetection: 254 nmTemperature: 25° C. With SiO2-supported amylose tris(3,5-dimethylbenzoyl)carbamate in hexane, isopropyl alcohol, T= 25 °C , Resolution of racemate, Product distribution / selectivity Patent; Daicel Chemical Industries, Ltd.; US7683167; (2010); (B2) English View in Reaxys 1-6 :The optical resolution of ten kinds of racemic bodies (FIG. 3) with the column-1 obtained by the above-mentioned operation (column temperature: about 20° C.) was performed. A HPLC pump (trade name: PU-980) manufactured by JASCO Corporation was used. The detection and identification of a peak were performed with a UV detector (wavelength: 254 nm, trade name: UV-970, manufactured by JASCO Corporation) and an optical rotation detector (trade name: OR-990, manufactured by JASCO Corporation) under the following conditions: a mixture of hexane and 2-propanol at a ratio of 95:5 was used as an eluent, and its flow rate was 0.2 ml/min. It should be noted that the number of theoretical plates N was determined from the peak of benzene, and a time to for which the eluent passed through the column was determined from the elution time of 1,3,5-tri-tert-butylbenzene.It should be noted that conditions concerning, for example, HPLC and a detector used in the evaluation for optical resolution identical to those described above were used in the following examples and comparative examples.Table 1 shows the results of the optical resolution with the column-1. Values in the table are a capacity ratio k1' and a separation factor α, and a sign in parentheses represents the optical activity of an enantiomer which was previously eluted.It should be noted that the capacity ratio k1' and the separation factor α are defined by the following formulae. A capacity ratio and a separation factor were calculated in the following examples and comparative examples by using the same formulae.Capacity ratio k1'k1'=[(retention time of enantiomer)-(t0)]/t0 [Num 1] Separation factor αα=(capacity ratio of enantiomer to be retained more strongly)/(capacity ratio of enantiomer to be retained more weakly) [Num 2]; [Table 1] TABLE 1 Optical resolutions of columns 1 to 4 Column-1a Column-2b Column-3a Column-4b Racemates k1' α k1' α k1' α k1' α 1 7.61(-) 1.30 5.97(-) 1.23 6.02(-) 1.23 4.30(-) 1.21 2 5.42(+) 1.58 5.13(+) 1.37 6.02(+) 1.09 3.69(+) 1.26 3 4.01(-)

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1.17 3.49(-) 1.76 3.34(-) 1.99 2.63(-) 1.74 4 11.49(+) 1.20 - 9.48(+) 1.19 5.63(+) 1.19 5 16.40(-) 3.90 7.96(-) 3.22 13.08(-) 2.80 5.38(-) 2.89 6 21.19(+) 1.26 13.59(+) 1.37 16.15(+) 1.43 9.08(+) 1.38 7 9.26(-) 1.13 7.44(-) 1.26 7.83(-) 1.29 5.57(-) 1.23 8 5.10(+) 1.26 2.35(+) 1.27 4.01(+) 1.27 - 9 20.00(-) 2.20 10.84(-) 2.50 24.13(-) 3.16 7.69(-) 2.57 10 20.75 1.00 6.63(+) 1.52 10.01(+) 1.91 4.12(+) 1.83 aEluent: hexane/2-propanol (95/5)bEluent: hexane/2-propanol (90/10) Column: 25 .x. 0.20 cm (i.d.), Flow rate: 0.2 ml/min With cellulose 3,5-dimethylphenylcarbamate in hexane, isopropyl alcohol, T= 20 °C , Resolution of racemate, Product distribution / selectivity Patent; Okamoto, Yoshio; Yamamoto, Chiyo; Ikai, Tomoyuki; Kamigaito, Masami; US2009/124798; (2009); (A1) English View in Reaxys 2-4 :The optical resolution of ten kinds of racemic bodies (FIG. 3) with the column-3 obtained by the above-mentioned operation were performed. The detection and identification of a peak were performed with a UV detector and an optical rotation detector under the following conditions: a mixture of hexane and 2-propanol at a ratio of 95:5 was used as an eluent, and its flow rate was 0.2 ml/min. It should be noted that the number of theoretical plates N was determined from the peak of benzene, and a time to for which the eluent passed through the column was determined from the elution time of 1,3,5-tri-tert-butylbenzene.Table 1 shows the results of the optical resolution with the column-3; [Table 1] TABLE 1 Optical resolutions of columns 1 to 4 Column-1a Column-2b Column-3a Column-4b Racemates k1' α k1' α k1' α k1' α 1 7.61(-) 1.30 5.97(-) 1.23 6.02(-) 1.23 4.30(-) 1.21 2 5.42(+) 1.58 5.13(+) 1.37 6.02(+) 1.09 3.69(+) 1.26 3 4.01(-) 1.17 3.49(-) 1.76 3.34(-) 1.99 2.63(-) 1.74 4 11.49(+) 1.20 - 9.48(+) 1.19 5.63(+) 1.19 5 16.40(-) 3.90 7.96(-) 3.22 13.08(-) 2.80 5.38(-) 2.89 6 21.19(+) 1.26 13.59(+) 1.37 16.15(+) 1.43 9.08(+) 1.38 7 9.26(-) 1.13 7.44(-) 1.26 7.83(-) 1.29 5.57(-) 1.23 8 5.10(+) 1.26 2.35(+) 1.27 4.01(+) 1.27 - 9 20.00(-) 2.20 10.84(-) 2.50 24.13(-) 3.16 7.69(-) 2.57 10 20.75 1.00 6.63(+) 1.52 10.01(+) 1.91 4.12(+) 1.83 aEluent: hexane/2-propanol (95/5)bEluent: hexane/2-propanol (90/10) Column: 25 .x. 0.20 cm (i.d.), Flow rate: 0.2 ml/min With cellulose 3,5-dimethylphenylcarbamate in hexane, isopropyl alcohol, Resolution of racemate, Product distribution / selectivity Patent; Okamoto, Yoshio; Yamamoto, Chiyo; Ikai, Tomoyuki; Kamigaito, Masami; US2009/124798; (2009); (A1) English View in Reaxys 2-5 :The optical resolution of nine kinds of racemic bodies (FIG. 3) with the column-2 obtained by the above-mentioned operation was performed. The detection and identification of a peak were performed with a UV detector and an optical rotation detector under the following conditions: a mixture of hexane and 2-propanol at a ratio of 90:10 was used as an eluent, and its flow rate was 0.2 ml/min. It should be noted that the number of theoretical plates N was determined from the peak of benzene, and a time to for which the eluent passed through the column was determined from the elution time of 1,3,5-tri-tert-butylbenzene.Table 1 shows the results of the optical resolution with the column-2. Values in the table are a capacity ratio k1' and a separation factor α, and a sign in parentheses represents the optical activity of an enantiomer which was previously eluted; [Table 1] TABLE 1 Optical resolutions of columns 1 to 4 Column-1a Column-2b Column-3a Column-4b Racemates k1' α k1' α k1' α k1' α 1 7.61(-) 1.30 5.97(-) 1.23 6.02(-) 1.23 4.30(-) 1.21 2 5.42(+) 1.58 5.13(+) 1.37 6.02(+) 1.09 3.69(+) 1.26 3 4.01(-) 1.17 3.49(-) 1.76 3.34(-) 1.99 2.63(-) 1.74 4 11.49(+) 1.20 - 9.48(+) 1.19 5.63(+) 1.19 5 16.40(-) 3.90 7.96(-) 3.22 13.08(-) 2.80 5.38(-) 2.89 6 21.19(+) 1.26 13.59(+) 1.37 16.15(+) 1.43 9.08(+) 1.38 7 9.26(-) 1.13 7.44(-) 1.26 7.83(-) 1.29 5.57(-) 1.23 8 5.10(+) 1.26 2.35(+) 1.27 4.01(+) 1.27 - 9 20.00(-) 2.20 10.84(-) 2.50 24.13(-) 3.16 7.69(-) 2.57 10 20.75 1.00 6.63(+) 1.52 10.01(+) 1.91 4.12(+) 1.83 aEluent: hexane/2-propanol (95/5)bEluent: hexane/2-propanol (90/10) Column: 25 .x. 0.20 cm (i.d.), Flow rate: 0.2 ml/min With cellulose 3,5-dimethylphenylcarbamate in hexane, isopropyl alcohol, Resolution of racemate, Product distribution / selectivity Patent; Okamoto, Yoshio; Yamamoto, Chiyo; Ikai, Tomoyuki; Kamigaito, Masami; US2009/124798; (2009); (A1) English View in Reaxys 3-4 :The optical resolution of nine kinds of racemic bodies (FIG. 3) with the column-4 obtained by the above-mentioned operation was performed. The detection and identification of a peak were performed with a UV detector and an optical rotation detector under the following conditions: a mixture of hexane and 2-propanol at a ratio of 90:10 was used as an eluent, and its flow rate was 0.1 ml/min. It should be noted that the number of theoretical plates N was determined from the peak of benzene, and a time to for which the eluent passed through the column was determined from the elution time of 1,3,5-tri-tert-butylbenzene. Table 1 shows the results of the optical resolution with the

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column-4.[Table 1] TABLE 1 Optical resolutions of columns 1 to 4 Column-1a Column-2b Column-3a Column-4b Racemates k1' α k1' α k1' α k1' α 1 7.61(-) 1.30 5.97(-) 1.23 6.02(-) 1.23 4.30(-) 1.21 2 5.42(+) 1.58 5.13(+) 1.37 6.02(+) 1.09 3.69(+) 1.26 3 4.01(-) 1.17 3.49(-) 1.76 3.34(-) 1.99 2.63(-) 1.74 4 11.49(+) 1.20 - 9.48(+) 1.19 5.63(+) 1.19 5 16.40(-) 3.90 7.96(-) 3.22 13.08(-) 2.80 5.38(-) 2.89 6 21.19(+) 1.26 13.59(+) 1.37 16.15(+) 1.43 9.08(+) 1.38 7 9.26(-) 1.13 7.44(-) 1.26 7.83(-) 1.29 5.57(-) 1.23 8 5.10(+) 1.26 2.35(+) 1.27 4.01(+) 1.27 - 9 20.00(-) 2.20 10.84(-) 2.50 24.13(-) 3.16 7.69(-) 2.57 10 20.75 1.00 6.63(+) 1.52 10.01(+) 1.91 4.12(+) 1.83 aEluent: hexane/2-propanol (95/5)bEluent: hexane/2-propanol (90/10) Column: 25 .x. 0.20 cm (i.d.), Flow rate: 0.2 ml/min With cellulose 3,5-dimethylphenylcarbamate in hexane, isopropyl alcohol, Resolution of racemate, Product distribution / selectivity Patent; Okamoto, Yoshio; Yamamoto, Chiyo; Ikai, Tomoyuki; Kamigaito, Masami; US2009/124798; (2009); (A1) English View in Reaxys 4 :Example 4[Production of Column for HPLC With CSP-2]CSP-2 (3.5 g) was dispersed in methanol, and then a stainless column having a diameter of 0.46 cm and a length of 25 cm was filled with the resultant slurry according to a slurry mode. Thus, a column filled with CSP-2 was produced.CSP-2 was evaluated for its asymmetry recognition ability with the resultant column under four kinds of evaluation conditions. The racemic bodies of Compounds 1 to 9 were used as samples for evaluation. The following evaluation of the chiral stationary phase for its asymmetry recognition ability is described for the respective evaluation conditions.[Evaluation (1)]The evaluation for the asymmetry recognition ability was performed with nine kinds of samples for evaluation (Compound Nos.: 1, 2, 3, 4, 5, 6, 7, 8, and 9) under the following conditions by HPLC. Table 5 shows the results of the evaluation. In addition, FIGS. 22 to 30 illustrate the chromatograms of the respective samples for evaluation.

With CSP-2 column in hexane, isopropyl alcohol, T= 25 °C , Resolution of racemate, Product distribution / selectivity Patent; Ema, Tadashi; Sakai, Takashi; Tanida, Daisuke; Sugita, Kyoko; Ohnishi, Atsushi; Miyazawa, Kenichiro; US2010/292464; (2010); (A1) English View in Reaxys Reaction Steps: 2 1: pyridine; sodium iodide / hexane; acetonitrile / 20 h / 20 °C 2: (R)-N-(5,5,4,4,3,3,2,2-octafluoropentyl)-tert-butanesulfinamide; 2,6-di- tert-butylphenol; 2,4-dinitrobenzenesulfonic acid; sodium sulfate / toluene / -78 - -50 °C With pyridine, 2,6-di- tert-butylphenol, 2,4-dinitrobenzenesulfonic acid, (R)-N-(5,5,4,4,3,3,2,2-octafluoropentyl)-tertbutanesulfinamide, sodium sulfate, sodium iodide in hexane, toluene, acetonitrile Beck, Elizabeth M.; Hyde, Alan M.; Jacobsen, Eric N.; Organic Letters; vol. 13; nb. 16; (2011); p. 4260 - 4263 View in Reaxys Reaction Steps: 2 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran; hexane / -78 - 20 °C / Inert atmosphere 1.2: 0 - 20 °C / Inert atmosphere 2.1: silver tetrafluoroborate; (R)-BINAP(AuCl)2 / propan-1-ol; dichloromethane / 16 h / 20 °C / Inert atmosphere With silver tetrafluoroborate, n-butyllithium, (R)-BINAP(AuCl)2, diisopropylamine in tetrahydrofuran, propan-1-ol, hexane, dichloromethane Cheon, Cheol Hong; Kanno, Osamu; Toste, F. Dean; Journal of the American Chemical Society; vol. 133; nb. 34; (2011); p. 13248 - 13251 View in Reaxys With C49H76N4O4, 3-chloro-benzenecarboperoxoic acid, scandium tris(trifluoromethanesulfonate) in ethyl acetate, Time= 18h, T= -20 °C , Baeyer-Villiger Ketone Oxidation, Reagent/catalyst, Temperature, Time, enantioselective reaction Zhou, Lin; Liu, Xiaohua; Ji, Jie; Zhang, Yuheng; Hu, Xiaolei; Lin, Lili; Feng, Xiaoming; Journal of the American Chemical Society; vol. 134; nb. 41; (2012); p. 17023 - 17026,4 View in Reaxys With C49H76N4O4, 3-chloro-benzenecarboperoxoic acid, scandium tris(trifluoromethanesulfonate) in ethyl acetate, Time= 18h, T= -20 °C , Baeyer-Villiger Ketone Oxidation, enantioselective reaction

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Zhou, Lin; Liu, Xiaohua; Ji, Jie; Zhang, Yuheng; Hu, Xiaolei; Lin, Lili; Feng, Xiaoming; Journal of the American Chemical Society; vol. 134; nb. 41; (2012); p. 17023 - 17026 View in Reaxys With Xylan Phenylcarbamate Derivative coated on theaminopropylsilanized silica gel. Column: 25 cm x 0.20 cm ID in hexane, isopropyl alcohol, Resolution of racemate, Reagent/catalyst Li, Geng; Shen, Jun; Li, Qiang; Okamoto, Yoshio; Chirality; vol. 27; nb. 8; (2015); p. 518 - 522 View in Reaxys With chiral poly(phenylacetylene)polymer coated on aminopropyl silanized silica gel in hexane, isopropyl alcohol, Resolution of racemate, Reagent/catalyst Zhang, Chunhong; Ma, Rui; Wang, Hailun; Sakai, Ryosuke; Satoh, Toshifumi; Kakuchi, Toyoji; Liu, Lijia; Okamoto, Yoshio; Chirality; vol. 27; nb. 8; (2015); p. 500 - 506 View in Reaxys With cellulose derivative which bears a fullerene (C60) moiety at the 6-position-based chiral stationary phase in hexane, isopropyl alcohol, T= 25 °C , Resolution of racemate Gao, Bo; Xu, Zeyu; Fan, Luan; Xu, Xiaodong; Bai, Jianwei; Shen, Xiande; Chemistry Letters; vol. 44; nb. 11; (2015); p. 1479 - 1481 View in Reaxys With high-performance liquid chromatography column with poly[diphenylacetylene, (h-poly-(2S0.36-co-30.64))]-based chiral stationary phases in hexane, isopropyl alcohol, Resolution of racemate, enantioselective reaction Maeda, Katsuhiro; Maruta, Miyuki; Sakai, Yuki; Ikai, Tomoyuki; Kanoh, Shigeyoshi; Molecules; vol. 21; nb. 11; (2016); Art.No: 1487 View in Reaxys With 3‐aminopropyl silica gel treated with amylose 2‐benzoate‐3‐(3,5-dimethylphenylcarbamate)‐6‐(phenylcarbamate) in hexane, isopropyl alcohol, Resolution of racemate, Reagent/catalyst, Solvent Tang, Shouwan; Jin, Zhaolei; Sun, Baishen; Wang, Fang; Tang, Wenyuan; Chirality; vol. 29; nb. 9; (2017); p.

512 - 521 View in Reaxys

O

O

O

O

O

Rx-ID: 44341580 View in Reaxys 2/46 Yield

Conditions & References With 2-oxo-Δ3-4,5,5-trimethylcyclopentenylacetyl-coenzyme A monooxygenase from Pseudomonas putida NCIMB 10007, NADPH, Enzymatic reaction, Baeyer-Villiger Ketone Oxidation, enantioselective reaction Rudroff, Florian; Fink, Michael J.; Pydi, Ramana; Bornscheuer, Uwe T.; Mihovilovic, Marko D.; Monatshefte fur Chemie; vol. 148; nb. 1; (2017); p. 157 - 165 View in Reaxys

O

O

O

O

Rx-ID: 44341581 View in Reaxys 3/46 Yield

Conditions & References With camphor monooxygenase from Cylindrocarpon radicicola ATCC 11011, NADPH, Enzymatic reaction, BaeyerVilliger Ketone Oxidation, enantioselective reaction

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Rudroff, Florian; Fink, Michael J.; Pydi, Ramana; Bornscheuer, Uwe T.; Mihovilovic, Marko D.; Monatshefte fur Chemie; vol. 148; nb. 1; (2017); p. 157 - 165 View in Reaxys

O

Si

O

O

Rx-ID: 4075103 View in Reaxys 4/46 Yield

Conditions & References With (R)-binaphthol-SnCl4 in dichloromethane, Time= 0.0833333h, T= -100 °C , enantioselective protonation silyl enol ethers and ketene bis(trialkylsilyl) acetals; var. solv, temp.

Ishihara, Kazuaki; Kaneeda, Masanobu; Yamamoto, Hisashi; Journal of the American Chemical Society; vol.

116; nb. 24; (1994); p. 11179 - 11180 View in Reaxys With (R,R)-2-phenyloctahydrobenzolt;1,3,2gt;diazaborole, multistep reaction, various chiral aminoboranes, Product distribution Yanagisawa, Akira; Inanami, Hiroshi; Yamamoto, Hisashi; Chemical Communications; nb. 15; (1998); p. 1573 1574 View in Reaxys With 2.6-dimethylphenol, tin(IV) chloride, (Ra)-1-(2-methoxynaphthalen-1-yl)naphthalen-2-ol in dichloromethane, toluene, Time= 0.0833333h, T= -80 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Ishihara; Nakamura; Kaneeda; Yamamoto; Journal of the American Chemical Society; vol. 118; nb. 50; (1996); p.

12854 - 12855 View in Reaxys With n-butyllithium, (R,R)-2-phenyloctahydrobenzolt;1,3,2gt;diazaborole, 1.) THF, hexane, 0 deg C, 2.) THF, hexane, toluene, -78 deg C, 2 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Yanagisawa, Akira; Inanami, Hiroshi; Yamamoto, Hisashi; Chemical Communications; nb. 15; (1998); p. 1573 1574 View in Reaxys With R-(-)-2-methoxy-2-phenyl ethanol, titanium tetrachloride in dichloromethane, Time= 1h, T= -78 °C , Product distribution, Further Variations: Reagents, Temperatures, time Nakashima, Daisuke; Yamamoto, Hisashi; Synlett; nb. 1; (2006); p. 150 - 152; Art.No: Y07805ST View in Reaxys With (S)-{3,3'-bis(4-t-butyl-2,6-diisopropylphenyl)-1,1'-binaphthalen-2,2'-yl}-N-triflyl-thiophosphoramide, phenol in toluene, Time= 8h, T= 20 °C , Inert atmosphere, Reactivity, Solvent, Reagent/catalyst, Time, Concentration, optical yield given as percent ee, enantioselective reaction Cheol, Hong Cheon; Yamamoto, Hisashi; Journal of the American Chemical Society; vol. 130; nb. 29; (2008); p.

9246 - 9247 View in Reaxys With methanol, (S)-2′-(diphenylphosphino)-1,1′-binaphthyl-2-ol, lanthanum(lll) triflate in dichloromethane, Time= 18h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Cheon, Cheol Hong; Imahori, Tatsushi; Yamamoto, Hisashi; Chemical Communications; vol. 46; nb. 37; (2010); p. 6980 - 6982 View in Reaxys With 2,6-di- tert-butylphenol, 2,4-dinitrobenzenesulfonic acid, (R)-N-(5,5,4,4,3,3,2,2-octafluoropentyl)-tert-butanesulfinamide, sodium sulfate in toluene, T= -78 - -50 °C , optical yield given as percent ee, enantioselective reaction

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Beck, Elizabeth M.; Hyde, Alan M.; Jacobsen, Eric N.; Organic Letters; vol. 13; nb. 16; (2011); p. 4260 - 4263 View in Reaxys With silver tetrafluoroborate, (R)-BINAP(AuCl)2 in propan-1-ol, dichloromethane, Time= 16h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Cheon, Cheol Hong; Kanno, Osamu; Toste, F. Dean; Journal of the American Chemical Society; vol. 133; nb. 34; (2011); p. 13248 - 13251 View in Reaxys With (R)-3,3′-dibromo vanol in toluene, Time= 2h, T= 20 °C , UV-irradiation, Solvent, Temperature, Overall yield = 64 percentSpectr.; enantioselective reaction Das, Anjan; Ayad, Suliman; Hanson, Kenneth; Organic Letters; vol. 18; nb. 20; (2016); p. 5416 - 5419 View in Reaxys

O

Si

O

O

Rx-ID: 28154864 View in Reaxys 5/46 Yield

Conditions & References With (S)-{3,3'-bis(2,4,6-triisopropylphenyl)-1,1'-binaphthalen-2,2'-yl}-N-triflyl-thiophosphoramide, acetic acid in toluene, Time= 12h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Cheol, Hong Cheon; Yamamoto, Hisashi; Journal of the American Chemical Society; vol. 130; nb. 29; (2008); p.

9246 - 9247 View in Reaxys With (R)-3,3′-dibromo vanol in toluene, Time= 2h, T= 20 °C , UV-irradiation, Overall yield = 78 percentSpectr.; enantioselective reaction Das, Anjan; Ayad, Suliman; Hanson, Kenneth; Organic Letters; vol. 18; nb. 20; (2016); p. 5416 - 5419 View in Reaxys

Si

O

O

O

Rx-ID: 31549573 View in Reaxys 6/46 Yield

Conditions & References With C19H25F6N3O2S, 2,4-dinitrobenzenesulfonic acid in toluene, T= -78 - -40 °C , optical yield given as percent ee, enantioselective reaction Beck, Elizabeth M.; Hyde, Alan M.; Jacobsen, Eric N.; Organic Letters; vol. 13; nb. 16; (2011); p. 4260 - 4263 View in Reaxys With (R)-3,3′-dibromo vanol in toluene, Time= 2h, T= 20 °C , UV-irradiation, Overall yield = 64 percentSpectr.; enantioselective reaction Das, Anjan; Ayad, Suliman; Hanson, Kenneth; Organic Letters; vol. 18; nb. 20; (2016); p. 5416 - 5419 View in Reaxys

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O

Si

O

O

Rx-ID: 44507222 View in Reaxys 7/46 Yield

Conditions & References With (R)-3,3′-dibromo vanol in toluene, Time= 2h, T= 20 °C , UV-irradiation, Overall yield = 61 percent; Overall yield = 0.1 g; enantioselective reaction Das, Anjan; Ayad, Suliman; Hanson, Kenneth; Organic Letters; vol. 18; nb. 20; (2016); p. 5416 - 5419 View in Reaxys

OH

O

Rx-ID: 9393818 View in Reaxys 8/46 Yield 100 %

Conditions & References With sodium hypochlorite, 9-azabicyclolt;3.3.1gt;nonane-N-oxyl, tetrabutylammomium bromide, sodium hydrogencarbonate, potassium bromide in dichloromethane, water, Time= 0.333333h, T= 0 °C Shibuya, Masatoshi; Tomizawa, Masaki; Sasano, Yusuke; Iwabuchi, Yoshiharu; Journal of Organic Chemistry; vol. 74; nb. 12; (2009); p. 4619 - 4622 View in Reaxys

99 %

With sodium hypochlorite, 1-methyl-2-azaadamantane-N-oxyl, tetrabutylammomium bromide, potassium bromide in dichloromethane, sodium hydrogencarbonate, Time= 0.333333h, T= 0 °C Shibuya, Masatoshi; Tomizawa, Masaki; Suzuki, Iwao; Iwabuchi, Yoshiharu; Journal of the American Chemical Society; vol. 128; nb. 26; (2006); p. 8412 - 8413 View in Reaxys

99 %

3.2.3 :Then, using 1-methyl-AZADO synthesized, the activities thereof as an oxidation catalyst were estimated in the same manner using various secondary alcohols specified in Tables 2 and 3. As for the reaction conditions, the catalyst amount was 0.01 eq. in CH2Cl2, and KBr (0.1 eq.), n-Bu4NBr (0.05 eq.) and NaOCl (1.4 eq.) were further added, and the reaction was carried out under ice cooling. The reaction time was 20 minutes. After completion of the reaction, the percent yield of each product was determined. The percent yield was calculated by the formula: (actual yield, i.e., the amount of product)/(theoretical yield, i.e., calculated from the amount of consumed starting material) x 100 (percent). For comparative examples, runs were carried out under the same reaction conditions using TEMPO, and each comparative yield was calculated. The results thus obtained are shown in Tables 2 and 3. Table 2 [Show Image] Test No. Alcohol species Yield (percent) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-1[Show Image] 84 83 2-2[Show Image] 91 5 2-3[Show Image] 99 16 2-4[Show Image] 93 15 2-5[Show Image] 100 8 2-6[Show Image] 100 12Table 3 Test No. Alcohol species Yield (percent) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-7[Show Image] 99 84 2-8[Show Image] 92 68 2-9[Show Image] 89 0 2-10[Show Image] 88 0 2-11[Show Image] 91 5 In the case of secondary alcohols having a relatively simple steric configuration (e.g. Test No. 2-1 and No. 2-7), the use of 1-methyl-AZADO of the invention as an oxidation catalyst and the use of TEMPO for comparison both gave target products in high yields. On the other hand, in the case of secondary alcohols having a sterically bulky, complicated structure, it was found that the use of 1-methyl-AZADO of the invention resulted in rapid oxidation, giving target products in high yields, whereas the use of TEMPO for comparison gave target products only in low yields. In view of such results, it is evident that 1-methyl-AZADO is a catalyst useful as an oxidation catalyst not only for primary alcohols but also secondary alcohols.

With sodium hypochlorite, tetrabutylammomium bromide, potassium bromide, 1-methyl-2-azaadamantane-N-oxyl in dichloromethane, Time= 0.333333h, T= 0 °C , Product distribution / selectivity Patent; TOHOKU UNIVERSITY; EP1775296; (2007); (A1) English View in Reaxys

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99 %

1 :Then, using the prepared ABNO, its activity as an oxidation catalyst was examined in the same manner with respect to various secondary alcohols as identified in Table 2. As the reaction conditions, the amount of the catalyst was 0.01 equivalent amount, in CH2Cl2, 0.1 equivalent amount of KBr, 0.05 equivalent amount of n-Bu4NBr and 1.5 equivalent amount of NaOCl were further added, and the reaction was carried out under cooling with ice for 20 minutes. After completion of the reaction, the yield of the product was determined. The yield was calculated from (the amount of substance of the product)/(the amount of substance of the raw material).x.100percent. As Comparative Examples, the same reaction was carried out using TEMPO or 1-methyl-AZADO under the same reaction conditions to determined the yield. The obtained results are shown in Table 2.With respect to a secondary alcohol having a sterically bulky and complicated structure, the yield of an aimed product is low in a Comparative Example in which TEMPO is used, but by ABNO of the present invention, the secondary alcohol is quickly oxidized to form an aimed product with high yield at the same level as a case of using 1-methyl-AZADO. With sodium hypochlorite, tetrabutylammomium bromide, sodium hydrogencarbonate, potassium bromide, 9-azabicyclolt;3.3.1gt;nonane-N-oxyl in dichloromethane, water, Time= 0.333333h, T= 0 °C , Product distribution / selectivity Patent; Nissan Chemical Industries Ltd.; US2008/221331; (2008); (A1) English View in Reaxys

99 %

1 :Then, using the prepared ABNO, its activity as an oxidation catalyst was examined in the same manner with respect to various secondary alcohols as identified in Table 2. As the reaction conditions, the amount of the catalyst was 0.01 equivalent amount, in CH2Cl2, 0.1 equivalent amount of KBr, 0.05 equivalent amount of n-Bu4NBr and 1.5 equivalent amount of NaOCl were further added, and the reaction was carried out under cooling with ice for 20 minutes. After completion of the reaction, the yield of the product was determined. The yield was calculated from (the amount of substance of the product)/(the amount of substance of the raw material).x.100percent. As Comparative Examples, the same reaction was carried out using TEMPO or 1-methyl-AZADO under the same reaction conditions to determined the yield. The obtained results are shown in Table 2.With respect to a secondary alcohol having a sterically bulky and complicated structure, the yield of an aimed product is low in a Comparative Example in which TEMPO is used, but by ABNO of the present invention, the secondary alcohol is quickly oxidized to form an aimed product with high yield at the same level as a case of using 1-methyl-AZADO. With sodium hypochlorite, tetrabutylammomium bromide, sodium hydrogencarbonate, potassium bromide, 1-methyl-2-azatricyclo[3.3.1.13,7]dec-2-yloxidanyl in dichloromethane, water, Time= 0.333333h, T= 0 °C , Product distribution / selectivity Patent; Nissan Chemical Industries Ltd.; US2008/221331; (2008); (A1) English View in Reaxys

99 %

With sodium hypochlorite, 1-methyl-2-azaadamantan-N-oxyl, tetrabutylammomium bromide, sodium hydrogencarbonate, potassium bromide in dichloromethane, water, Time= 0.333333h, T= 0 °C , Inert atmosphere Shibuya, Masatoshi; Sasano, Yusuke; Tomizawa, Masaki; Hamada, Toshimasa; Kozawa, Masami; Nagahama, Noriaki; Iwabuchi, Yoshiharu; Synthesis; nb. 21; (2011); p. 3418 - 3425; Art.No: F76611SS View in Reaxys

99 %

With octahydro-2,5-epiminopentalen-7-yloxidanyl, acetic acid, sodium nitrite in acetonitrile, Time= 4h, T= 20 °C , air Hayashi, Masaki; Sasano, Yusuke; Nagasawa, Shota; Shibuya, Masatoshi; Iwabuchi, Yoshiharu; Chemical and Pharmaceutical Bulletin; vol. 59; nb. 12; (2011); p. 1570 - 1573 View in Reaxys

99.4%

6.f : Example 6: Oxidation of alcohols using air as bulk oxidant; (f) Oxidation of trans-2-phenylcyclohexanol [0071] [0072] trans-2-Phenylcyclohexanol (63.4 mg, 0.360 mmol) was oxidized in the same manner as that described in Example 6, (a) to obtain the objective compound (62.4 mg; yield, 99.4percent).1H-NMR (400 MHz, CDCl3): δ 7.35-7.13 (m, 5H), 3.61 (dd, J=12.1, 5.3 Hz, 1H), 2.53-2.45 (m, 2H), 2.30-2.25 (m, 1H), 2.17-2.15 (m, 1H), 2.06-1.99 (m, 2H), 1.86-1.80 (m, 2H). 13C-NMR (100 MHz, CDCl3): δ 210.2, 138.7, 128.5, 128.3, 126.8, 57.3, 42.1, 35.0, 27.8, 25.3.IR (CHCl3, cm-1): 1700.EI-MS m/z: 174 (M+)HRMS (EI): Calcd. for C12H14O: 174.1045, Found: 174.1058. ; A solution of 4-phenylbutan-2-ol (104.3 mg, 0.694 mmol), Nor-AZADO (0.96 mg, 6.94 µmol), and acetic acid (79.5 µl, 1.389 mmol) in acetonitrile (0.69 ml) was added with sodium nitrite (9.58 mg, 0.139 mmol), and the mixture was stirred at room temperature for 4 hours under an air atmosphere. The reaction mixture was added with saturated aqueous sodium carbonate (2 ml), and the mixture was extracted with dichloromethane. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the objective compound (101.1 mg; yield, 98.3percent). The spectrum data were found to be the same as those obtained in Example 5, (b).

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With 9-benzyl-9-norazaadamantane N-oxyl, oxygen, acetic acid, sodium nitrite in acetonitrile, Time= 5h, T= 20 °C , Catalytic behavior Patent; Tohoku University; IWABUCHI Yoshiharu; HAYASHI Masaki; EP2594550; (2013); (A1) English View in Reaxys 97 %

With dmap, [2,2]bipyridinyl, 2-azatricyclo[3.3.1.13,7]dec-2-yloxidanyl, copper(l) chloride in acetonitrile, Time= 8h, T= 20 °C , Reagent/catalyst Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu; Chemistry An Asian Journal; vol. 10; nb. 4; (2015); p. 1004 - 1009 View in Reaxys

92 %

With N-Bromosuccinimide, N-(phenylthio)-N-(tert-butyl)amine, potassium carbonate, 4 A molecular sieve in dichloromethane, Time= 24h, T= 20 °C Matsuo, Jun-Ichi; Iida, Daisuke; Yamanaka, Hiroyuki; Mukaiyama, Teruaki; Tetrahedron; vol. 59; nb. 35; (2003); p. 6739 - 6750 View in Reaxys

88.9 %

With pyridinium chlorochromate in dichloromethane, Time= 15h, Inert atmosphere, Molecular sieve Leung, Diana; Anslyn, Eric V.; Organic Letters; vol. 13; nb. 9; (2011); p. 2298 - 2301 View in Reaxys

16 %

3.2.3 :Then, using 1-methyl-AZADO synthesized, the activities thereof as an oxidation catalyst were estimated in the same manner using various secondary alcohols specified in Tables 2 and 3. As for the reaction conditions, the catalyst amount was 0.01 eq. in CH2Cl2, and KBr (0.1 eq.), n-Bu4NBr (0.05 eq.) and NaOCl (1.4 eq.) were further added, and the reaction was carried out under ice cooling. The reaction time was 20 minutes. After completion of the reaction, the percent yield of each product was determined. The percent yield was calculated by the formula: (actual yield, i.e., the amount of product)/(theoretical yield, i.e., calculated from the amount of consumed starting material) x 100 (percent). For comparative examples, runs were carried out under the same reaction conditions using TEMPO, and each comparative yield was calculated. The results thus obtained are shown in Tables 2 and 3. Table 2 [Show Image] Test No. Alcohol species Yield (percent) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-1[Show Image] 84 83 2-2[Show Image] 91 5 2-3[Show Image] 99 16 2-4[Show Image] 93 15 2-5[Show Image] 100 8 2-6[Show Image] 100 12Table 3 Test No. Alcohol species Yield (percent) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-7[Show Image] 99 84 2-8[Show Image] 92 68 2-9[Show Image] 89 0 2-10[Show Image] 88 0 2-11[Show Image] 91 5 In the case of secondary alcohols having a relatively simple steric configuration (e.g. Test No. 2-1 and No. 2-7), the use of 1-methyl-AZADO of the invention as an oxidation catalyst and the use of TEMPO for comparison both gave target products in high yields. On the other hand, in the case of secondary alcohols having a sterically bulky, complicated structure, it was found that the use of 1-methyl-AZADO of the invention resulted in rapid oxidation, giving target products in high yields, whereas the use of TEMPO for comparison gave target products only in low yields. In view of such results, it is evident that 1-methyl-AZADO is a catalyst useful as an oxidation catalyst not only for primary alcohols but also secondary alcohols.

With sodium hypochlorite, tetrabutylammomium bromide, potassium bromide, 2,2,6,6-tetramethyl-piperidine-N-oxyl in dichloromethane, Time= 0.333333h, T= 0 °C , Product distribution / selectivity Patent; TOHOKU UNIVERSITY; EP1775296; (2007); (A1) English View in Reaxys

16 %

1 :Then, using the prepared ABNO, its activity as an oxidation catalyst was examined in the same manner with respect to various secondary alcohols as identified in Table 2. As the reaction conditions, the amount of the catalyst was 0.01 equivalent amount, in CH2Cl2, 0.1 equivalent amount of KBr, 0.05 equivalent amount of n-Bu4NBr and 1.5 equivalent amount of NaOCl were further added, and the reaction was carried out under cooling with ice for 20 minutes. After completion of the reaction, the yield of the product was determined. The yield was calculated from (the amount of substance of the product)/(the amount of substance of the raw material).x.100percent. As Comparative Examples, the same reaction was carried out using TEMPO or 1-methyl-AZADO under the same reaction conditions to determined the yield. The obtained results are shown in Table 2.With respect to a secondary alcohol having a sterically bulky and complicated structure, the yield of an aimed product is low in a Comparative Example in which TEMPO is used, but by ABNO of the present invention, the secondary alcohol is quickly oxidized to form an aimed product with high yield at the same level as a case of using 1-methyl-AZADO.

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With sodium hypochlorite, tetrabutylammomium bromide, sodium hydrogencarbonate, potassium bromide, 2,2,6,6Tetramethyl-1-piperidinyloxy free radical in dichloromethane, water, Time= 0.333333h, T= 0 °C , Product distribution / selectivity Patent; Nissan Chemical Industries Ltd.; US2008/221331; (2008); (A1) English View in Reaxys With pyridinium chlorochromate in dichloromethane, T= 5 °C Bui; Hansen; Stenstrom; Hudlicky; Ribbons; New Journal of Chemistry; vol. 25; nb. 1; (2001); p. 116 - 124 View in Reaxys

OH racemate

OH

O

O

Rx-ID: 40165607 View in Reaxys 9/46 Yield

Conditions & References

48 %

With trichloroisocyanuric acid, (1R,3S,6R,7S,8R)-7-benzyl-3-n-buthyl-4-oxa-5-azahomoadamantane, sodium hydrogencarbonate in dichloromethane, Time= 3h, T= -40 °C , Inert atmosphere Tomizawa, Masaki; Shibuya, Masatoshi; Iwabuchi, Yoshiharu; Organic Letters; vol. 16; nb. 18; (2014); p. 4968 4968 View in Reaxys

Sn

O Cl

O

O

Rx-ID: 35428773 View in Reaxys 10/46 Yield

Conditions & References Stage 1: With (R)-2-(dicyclohexylphosphino)-2′-(2-naphthyloxy)-1,1'-binaphthyl, sodium acetate, palladium diacetate in diethyl ether, Time= 0.166667h, T= 25 °C , Glovebox, Inert atmosphere Stage 2: in diethyl ether, dodecane, Time= 48h, T= 50 °C , Glovebox, Inert atmosphere, Overall yield = 93 percent; Overall yield = 78 mg Huang, Zhiyan; Lim, Li Hui; Chen, Zuliang; Li, Yongxin; Zhou, Feng; Su, Haibin; Zhou, Jianrong; Angewandte Chemie - International Edition; vol. 52; nb. 18; (2013); p. 4906 - 4911; Angew. Chem.; (2013); p. 5006 - 5011,6 View in Reaxys

O

O

Rx-ID: 34395828 View in Reaxys 11/46 Yield

Conditions & References Reaction Steps: 5 1.1: sodium hydroxide / water / 0.08 h / 20 °C 1.2: 72 h 2.1: sodium tetrahydroborate / methanol / 2 h / 0 - 20 °C 3.1: C12H16ClO2Ru; candida antarcticalipase B; sodium carbonate / toluene; tetrahydrofuran / 0.17 h / 40 °C / Inert atmosphere; Schlenk technique 3.2: 48 h / Schlenk technique; Inert atmosphere 4.1: copper(l) chloride / 0.25 h / 0 °C / Schlenk technique; Inert atmosphere 4.2: Schlenk technique; Inert atmosphere 5.1: sodium periodate; rhodium(III) chloride hydrate / water; dichloromethane; acetonitrile / 20 °C / Inert atmosphere

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With sodium tetrahydroborate, sodium periodate, rhodium(III) chloride hydrate, candida antarcticalipase B, C12H16ClO2Ru, sodium carbonate, copper(l) chloride, sodium hydroxide in tetrahydrofuran, methanol, dichloromethane, water, toluene, acetonitrile, 1.2: |Aldol Condensation Warner, Madeleine C.; Nagendiran, Anuja; Bogár, Krisztián; Bäckvall, Jan-E.; Organic Letters; vol. 14; nb. 19; (2012); p. 5094 - 5097 View in Reaxys

OH E

O

Rx-ID: 34395856 View in Reaxys 12/46 Yield

Conditions & References Reaction Steps: 3 1.1: C12H16ClO2Ru; candida antarcticalipase B; sodium carbonate / toluene; tetrahydrofuran / 0.17 h / 40 °C / Inert atmosphere; Schlenk technique 1.2: 48 h / Schlenk technique; Inert atmosphere 2.1: copper(l) chloride / 0.25 h / 0 °C / Schlenk technique; Inert atmosphere 2.2: Schlenk technique; Inert atmosphere 3.1: sodium periodate; rhodium(III) chloride hydrate / water; dichloromethane; acetonitrile / 20 °C / Inert atmosphere With sodium periodate, rhodium(III) chloride hydrate, candida antarcticalipase B, C12H16ClO2Ru, sodium carbonate, copper(l) chloride in tetrahydrofuran, dichloromethane, water, toluene, acetonitrile Warner, Madeleine C.; Nagendiran, Anuja; Bogár, Krisztián; Bäckvall, Jan-E.; Organic Letters; vol. 14; nb. 19; (2012); p. 5094 - 5097 View in Reaxys

O E

O

Rx-ID: 34395872 View in Reaxys 13/46 Yield

Conditions & References Reaction Steps: 4 1.1: sodium tetrahydroborate / methanol / 2 h / 0 - 20 °C 2.1: C12H16ClO2Ru; candida antarcticalipase B; sodium carbonate / toluene; tetrahydrofuran / 0.17 h / 40 °C / Inert atmosphere; Schlenk technique 2.2: 48 h / Schlenk technique; Inert atmosphere 3.1: copper(l) chloride / 0.25 h / 0 °C / Schlenk technique; Inert atmosphere 3.2: Schlenk technique; Inert atmosphere 4.1: sodium periodate; rhodium(III) chloride hydrate / water; dichloromethane; acetonitrile / 20 °C / Inert atmosphere With sodium tetrahydroborate, sodium periodate, rhodium(III) chloride hydrate, candida antarcticalipase B, C12H16ClO2Ru, sodium carbonate, copper(l) chloride in tetrahydrofuran, methanol, dichloromethane, water, toluene, acetonitrile Warner, Madeleine C.; Nagendiran, Anuja; Bogár, Krisztián; Bäckvall, Jan-E.; Organic Letters; vol. 14; nb. 19; (2012); p. 5094 - 5097 View in Reaxys

O E

O

O

Rx-ID: 34395879 View in Reaxys 14/46

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Yield

Conditions & References Reaction Steps: 2 1.1: copper(l) chloride / 0.25 h / 0 °C / Schlenk technique; Inert atmosphere 1.2: Schlenk technique; Inert atmosphere 2.1: sodium periodate; rhodium(III) chloride hydrate / water; dichloromethane; acetonitrile / 20 °C / Inert atmosphere With sodium periodate, rhodium(III) chloride hydrate, copper(l) chloride in dichloromethane, water, acetonitrile Warner, Madeleine C.; Nagendiran, Anuja; Bogár, Krisztián; Bäckvall, Jan-E.; Organic Letters; vol. 14; nb. 19; (2012); p. 5094 - 5097 View in Reaxys

E

O

Rx-ID: 34395893 View in Reaxys 15/46 Yield

Conditions & References

73 %

With sodium periodate, rhodium(III) chloride hydrate in dichloromethane, water, acetonitrile, T= 20 °C , Inert atmosphere, enantioselective reaction Warner, Madeleine C.; Nagendiran, Anuja; Bogár, Krisztián; Bäckvall, Jan-E.; Organic Letters; vol. 14; nb. 19; (2012); p. 5094 - 5097 View in Reaxys

O

O O O

O

O

O

Rx-ID: 34568088 View in Reaxys 16/46 Yield

Conditions & References With C49H76N4O4, 3-chloro-benzenecarboperoxoic acid, scandium tris(trifluoromethanesulfonate) in ethyl acetate, Time= 24h, T= 0 °C , Baeyer-Villiger Ketone Oxidation, Reagent/catalyst, enantioselective reaction Zhou, Lin; Liu, Xiaohua; Ji, Jie; Zhang, Yuheng; Hu, Xiaolei; Lin, Lili; Feng, Xiaoming; Journal of the American Chemical Society; vol. 134; nb. 41; (2012); p. 17023 - 17026 View in Reaxys With C49H76N4O4, aluminum isopropoxide, 3-chloro-benzenecarboperoxoic acid, scandium tris(trifluoromethanesulfonate) in ethyl acetate, Time= 24h, T= 0 °C , Baeyer-Villiger Ketone Oxidation, Reagent/catalyst, enantioselective reaction Zhou, Lin; Liu, Xiaohua; Ji, Jie; Zhang, Yuheng; Hu, Xiaolei; Lin, Lili; Feng, Xiaoming; Journal of the American Chemical Society; vol. 134; nb. 49; (2012); p. 20208 - 20208 View in Reaxys

O

O

O

O

O

Rx-ID: 34568089 View in Reaxys 17/46 Yield 51 %

Conditions & References With scandium isopropoxide, C49H76N4O4, 3-chloro-benzenecarboperoxoic acid, scandium tris(trifluoromethanesulfonate) in ethyl acetate, Time= 24h, T= 0 °C , Baeyer-Villiger Ketone Oxidation, enantioselective reaction

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Zhou, Lin; Liu, Xiaohua; Ji, Jie; Zhang, Yuheng; Hu, Xiaolei; Lin, Lili; Feng, Xiaoming; Journal of the American Chemical Society; vol. 134; nb. 41; (2012); p. 17023 - 17026 View in Reaxys 51 %

With scandium isopropoxide, C49H76N4O4, 3-chloro-benzenecarboperoxoic acid, scandium tris(trifluoromethanesulfonate) in ethyl acetate, Time= 24h, T= -10 °C , Baeyer-Villiger Ketone Oxidation, enantioselective reaction Zhou, Lin; Liu, Xiaohua; Ji, Jie; Zhang, Yuheng; Hu, Xiaolei; Lin, Lili; Feng, Xiaoming; Journal of the American Chemical Society; vol. 134; nb. 49; (2012); p. 20208 - 20208 View in Reaxys

O

Si

O

Rx-ID: 10200355 View in Reaxys 18/46 Yield

Conditions & References

96 %

With methanol, silver fluoride, (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl in dichloromethane, Time= 24h, T= -30 °C Yanagisawa, Akira; Touge, Taichiro; Arai, Takayoshi; Angewandte Chemie - International Edition; vol. 44; nb. 10; (2005); p. 1546 - 1548 View in Reaxys

96 %

With silver tetrafluoroborate, (R)-BINAP(AuCl)2 in ethanol, dichloromethane, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Cheon, Cheol Hong; Kanno, Osamu; Toste, F. Dean; Journal of the American Chemical Society; vol. 133; nb. 34; (2011); p. 13248 - 13251 View in Reaxys

Si

O

O

O

Rx-ID: 31549574 View in Reaxys 19/46 Yield

Conditions & References With C19H25F6N3O2S, 2,4-dinitrobenzenesulfonic acid in toluene, T= -78 - -40 °C , optical yield given as percent ee, enantioselective reaction Beck, Elizabeth M.; Hyde, Alan M.; Jacobsen, Eric N.; Organic Letters; vol. 13; nb. 16; (2011); p. 4260 - 4263 View in Reaxys

I

O

O

Rx-ID: 31549585 View in Reaxys 20/46 Yield

Conditions & References Reaction Steps: 3 1: tris-(dibenzylideneacetone)dipalladium(0); tributyltin fluoride; triethylamine; tri tert-butylphosphoniumtetrafluoroborate / benzene / 24 h / 80 °C / Inert atmosphere 2: pyridine; sodium iodide / hexane; acetonitrile / 20 h / 20 °C 3: (R)-N-(5,5,4,4,3,3,2,2-octafluoropentyl)-tert-butanesulfinamide; 2,6-di- tert-butylphenol; 2,4-dinitrobenzenesulfonic acid; sodium sulfate / toluene / -78 - -50 °C

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With pyridine, tris-(dibenzylideneacetone)dipalladium(0), 2,6-di- tert-butylphenol, 2,4-dinitrobenzenesulfonic acid, (R)N-(5,5,4,4,3,3,2,2-octafluoropentyl)-tert-butanesulfinamide, tributyltin fluoride, sodium sulfate, triethylamine, sodium iodide, tri tert-butylphosphoniumtetrafluoroborate in hexane, toluene, acetonitrile, benzene Beck, Elizabeth M.; Hyde, Alan M.; Jacobsen, Eric N.; Organic Letters; vol. 13; nb. 16; (2011); p. 4260 - 4263 View in Reaxys

Si

O

O

O

Rx-ID: 31549613 View in Reaxys 21/46 Yield

Conditions & References Reaction Steps: 3 1: tris-(dibenzylideneacetone)dipalladium(0); tributyltin fluoride; triethylamine; tri tert-butylphosphoniumtetrafluoroborate / benzene / 24 h / 80 °C / Inert atmosphere 2: pyridine; sodium iodide / hexane; acetonitrile / 20 h / 20 °C 3: (R)-N-(5,5,4,4,3,3,2,2-octafluoropentyl)-tert-butanesulfinamide; 2,6-di- tert-butylphenol; 2,4-dinitrobenzenesulfonic acid; sodium sulfate / toluene / -78 - -50 °C With pyridine, tris-(dibenzylideneacetone)dipalladium(0), 2,6-di- tert-butylphenol, 2,4-dinitrobenzenesulfonic acid, (R)N-(5,5,4,4,3,3,2,2-octafluoropentyl)-tert-butanesulfinamide, tributyltin fluoride, sodium sulfate, triethylamine, sodium iodide, tri tert-butylphosphoniumtetrafluoroborate in hexane, toluene, acetonitrile, benzene Beck, Elizabeth M.; Hyde, Alan M.; Jacobsen, Eric N.; Organic Letters; vol. 13; nb. 16; (2011); p. 4260 - 4263 View in Reaxys

O

O

Rx-ID: 31667206 View in Reaxys 22/46 Yield

Conditions & References Reaction Steps: 2 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran; hexane / -78 - 20 °C / Inert atmosphere 1.2: 0 - 20 °C / Inert atmosphere 2.1: silver tetrafluoroborate; (R)-BINAP(AuCl)2 / ethanol; dichloromethane / 20 °C / Inert atmosphere With silver tetrafluoroborate, n-butyllithium, (R)-BINAP(AuCl)2, diisopropylamine in tetrahydrofuran, ethanol, hexane, dichloromethane Cheon, Cheol Hong; Kanno, Osamu; Toste, F. Dean; Journal of the American Chemical Society; vol. 133; nb. 34; (2011); p. 13248 - 13251 View in Reaxys

O

O

O

Rx-ID: 29536818 View in Reaxys 23/46 Yield

Conditions & References With (R)-3,3'-bis(2,4,6-triisopropylphenyl)binol phosphoric acid, diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate in cyclohexane, Time= 72h, T= 50 °C , Molecular sieve, optical yield given as percent ee Wakchaure, Vijay N.; Zhou, Jian; Hoffmann, Sebastian; List, Benjamin; Angewandte Chemie - International Edition; vol. 49; nb. 27; (2010); p. 4612 - 4614 View in Reaxys

Copyright © 2018 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

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O

O

O

O

O

Rx-ID: 29716925 View in Reaxys 24/46 Yield

Conditions & References With Gln93Asn/Pro94Asp mutant phenylacetone monooxygenase, Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase, nicotinamide adenine dinucleotide, isopropyl alcohol in acetonitrile, T= 30 °C , pH= 8, aq. buffer, Baeyer-Villiger oxidation, optical yield given as percent ee, enantioselective reaction Wu, Sheng; Acevedo, Juan Pablo; Reetz, Manfred T.; Proceedings of the National Academy of Sciences of the United States of America; vol. 107; nb. 7; (2010); p. 2775 - 2780 View in Reaxys

OH

O

O

Rx-ID: 28537862 View in Reaxys 25/46 Yield

Conditions & References With potassium bromide in water, T= 20 °C , optical yield given as percent ee Takenaga, Naoko; Goto, Akihiro; Yoshimura, Misaki; Fujioka, Hiromichi; Dohi, Toshifumi; Kita, Yasuyuki; Tetrahedron Letters; vol. 50; nb. 26; (2009); p. 3227 - 3229 View in Reaxys

O

O

O

O

O

O

O

Rx-ID: 29153828 View in Reaxys 26/46 Yield

Conditions & References With phenylacetone monooxygenase Pro440Phe mutant, secondary alcohol dehydrogenase, NADP, isopropyl alcohol in acetonitrile, T= 30 °C , pH= 8, aq. buffer, Enzymatic reaction, Baeyer-Villiger oxidation, Kinetics, optical yield given as percent ee, enantioselective reaction Reetz, Manfred T.; Wu, Sheng; Journal of the American Chemical Society; vol. 131; nb. 42; (2009); p. 15424 15432 View in Reaxys

Si

Si

O

O

O

Rx-ID: 28154848 View in Reaxys 27/46 Yield

Conditions & References With (S)-{3,3'-bis(2,4,6-triisopropylphenyl)-1,1'-binaphthalen-2,2'-yl}-N-triflyl-thiophosphoramide, acetic acid in toluene, Time= 6h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Cheol, Hong Cheon; Yamamoto, Hisashi; Journal of the American Chemical Society; vol. 130; nb. 29; (2008); p.

9246 - 9247 View in Reaxys

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17/24

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Si

O

O

O

Rx-ID: 28154865 View in Reaxys 28/46 Yield

Conditions & References With (S)-{3,3'-bis(2,4,6-triisopropylphenyl)-1,1'-binaphthalen-2,2'-yl}-N-triflyl-thiophosphoramide, acetic acid in toluene, Time= 8h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Cheol, Hong Cheon; Yamamoto, Hisashi; Journal of the American Chemical Society; vol. 130; nb. 29; (2008); p.

9246 - 9247 View in Reaxys

OH

OH

O

Rx-ID: 28173321 View in Reaxys 29/46 Yield

Conditions & References

40 %

With [palladium(II)((-)-sparteine)dibromide], oxygen, caesium carbonate, (-)-sparteine in chloroform, Time= 49h, T= 23 °C , Molecular sieve, optical yield given as percent de Ebner, David C.; Trend, Raissa M.; Genet, Cedric; McGrath, Matthew J.; O'Brien, Peter; Stoltz, Brian M.; Angewandte Chemie - International Edition; vol. 47; nb. 34; (2008); p. 6367 - 6370 View in Reaxys

I O

I

O

O

O

Rx-ID: 11203845 View in Reaxys 30/46 Yield

Conditions & References Multistep reaction. Title compound not separated from byproducts.

Soorukram, Darunee; Knochel, Paul; Angewandte Chemie - International Edition; vol. 45; nb. 22; (2006); p. 3686 3689 View in Reaxys

I

O

Rx-ID: 11306877 View in Reaxys 31/46 Yield

Conditions & References Reaction Steps: 2 1.1: tert-butyllithium / tetrahydrofuran; pentane / 0.5 h / -78 °C 1.2: tetrahydrofuran; pentane / 0.5 h / -78 °C 2.1: HF*pyridine; pyridine / tetrahydrofuran / 0.5 h / 20 °C With pyridine, tert.-butyl lithium, pyridine hydrogenfluoride in tetrahydrofuran, pentane Soorukram, Darunee; Knochel, Paul; Angewandte Chemie - International Edition; vol. 45; nb. 22; (2006); p. 3686 3689

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View in Reaxys

O O

N

O

Rx-ID: 9908460 View in Reaxys 32/46 Yield

Conditions & References Stage 1: With sodium methylate in methanol, Time= 0.5h, T= 0 °C Stage 2: With sulfuric acid in methanol, Time= 1h, T= -20 °C Stage 3: With hydrogenchloride in dichloromethane, Time= 2h, T= 20 °C Dong, Lin; Xu, Yan-Jun; Cun, Lin-Feng; Cui, Xin; Mi, Ai-Qiao; Jiang, Yao-Zhong; Gong, Liu-Zhu; Organic Letters; vol. 7; nb. 19; (2005); p. 4285 - 4288 View in Reaxys

O O

N

O

Rx-ID: 12979999 View in Reaxys 33/46 Yield

Conditions & References Reaction Steps: 2 1.1: 98 percent / NaBH4 / ethanol / 2 h / 20 °C 2.1: MeONa / methanol / 0.5 h / 0 °C 2.2: H2SO4 / methanol / 1 h / -20 °C 2.3: aq. HCl / CH2Cl2 / 2 h / 20 °C With sodium tetrahydroborate, sodium methylate in methanol, ethanol Dong, Lin; Xu, Yan-Jun; Cun, Lin-Feng; Cui, Xin; Mi, Ai-Qiao; Jiang, Yao-Zhong; Gong, Liu-Zhu; Organic Letters; vol. 7; nb. 19; (2005); p. 4285 - 4288 View in Reaxys

O

N

O

O O

O

Rx-ID: 12981325 View in Reaxys 34/46 Yield

Conditions & References Reaction Steps: 3 1.1: (R)-BINAP; Rh(acac)(C2H4)2 / dioxane; H2O / 5 h / 100 °C 2.1: 98 percent / NaBH4 / ethanol / 2 h / 20 °C 3.1: MeONa / methanol / 0.5 h / 0 °C 3.2: H2SO4 / methanol / 1 h / -20 °C 3.3: aq. HCl / CH2Cl2 / 2 h / 20 °C With sodium tetrahydroborate, bis(ethylene)rhodium acetylacetonate, sodium methylate, (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl in 1,4-dioxane, methanol, ethanol, water Dong, Lin; Xu, Yan-Jun; Cun, Lin-Feng; Cui, Xin; Mi, Ai-Qiao; Jiang, Yao-Zhong; Gong, Liu-Zhu; Organic Letters; vol. 7; nb. 19; (2005); p. 4285 - 4288 View in Reaxys

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O

O O

N

O

O

Rx-ID: 13009543 View in Reaxys 35/46 Yield

Conditions & References Reaction Steps: 3 1.1: (R)-BINAP; Rh(acac)(C2H4)2 / dioxane; H2O / 5 h / 100 °C 2.1: 98 percent / NaBH4 / ethanol / 2 h / 20 °C 3.1: MeONa / methanol / 0.5 h / 0 °C 3.2: H2SO4 / methanol / 1 h / -20 °C 3.3: aq. HCl / CH2Cl2 / 2 h / 20 °C With sodium tetrahydroborate, bis(ethylene)rhodium acetylacetonate, sodium methylate, (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl in 1,4-dioxane, methanol, ethanol, water Dong, Lin; Xu, Yan-Jun; Cun, Lin-Feng; Cui, Xin; Mi, Ai-Qiao; Jiang, Yao-Zhong; Gong, Liu-Zhu; Organic Letters; vol. 7; nb. 19; (2005); p. 4285 - 4288 View in Reaxys

HO B HO O

Rx-ID: 13020085 View in Reaxys 36/46 Yield

Conditions & References Reaction Steps: 3 1.1: (R)-BINAP; Rh(acac)(C2H4)2 / dioxane; H2O / 5 h / 100 °C 2.1: 98 percent / NaBH4 / ethanol / 2 h / 20 °C 3.1: MeONa / methanol / 0.5 h / 0 °C 3.2: H2SO4 / methanol / 1 h / -20 °C 3.3: aq. HCl / CH2Cl2 / 2 h / 20 °C With sodium tetrahydroborate, bis(ethylene)rhodium acetylacetonate, sodium methylate, (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl in 1,4-dioxane, methanol, ethanol, water Dong, Lin; Xu, Yan-Jun; Cun, Lin-Feng; Cui, Xin; Mi, Ai-Qiao; Jiang, Yao-Zhong; Gong, Liu-Zhu; Organic Letters; vol. 7; nb. 19; (2005); p. 4285 - 4288 View in Reaxys Reaction Steps: 3 1.1: (R)-BINAP; Rh(acac)(C2H4)2 / dioxane; H2O / 5 h / 100 °C 2.1: 98 percent / NaBH4 / ethanol / 2 h / 20 °C 3.1: MeONa / methanol / 0.5 h / 0 °C 3.2: H2SO4 / methanol / 1 h / -20 °C 3.3: aq. HCl / CH2Cl2 / 2 h / 20 °C With sodium tetrahydroborate, bis(ethylene)rhodium acetylacetonate, sodium methylate, (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl in 1,4-dioxane, methanol, ethanol, water Dong, Lin; Xu, Yan-Jun; Cun, Lin-Feng; Cui, Xin; Mi, Ai-Qiao; Jiang, Yao-Zhong; Gong, Liu-Zhu; Organic Letters; vol. 7; nb. 19; (2005); p. 4285 - 4288 View in Reaxys

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20/24

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O

H 2N H

H N H

NH 2

O

O

NH 2

O

Rx-ID: 9641507 View in Reaxys 37/46 Yield

Conditions & References

40 %

With n-butyllithium in tetrahydrofuran, hexane, Time= 6h, T= 0 - 20 °C , Haller-Bauer reaction Ishihara, Kazuaki; Yano, Takayuki; Organic Letters; vol. 6; nb. 12; (2004); p. 1983 - 1986 View in Reaxys

O O

O

O

Rx-ID: 4676476 View in Reaxys 38/46 Yield

Conditions & References With samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, Time= 0.5h, Ambient temperature, effect of different chiral proton sources, Product distribution Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron Letters; vol. 38; nb. 15; (1997); p. 2709 - 2712 View in Reaxys With samarium diiodide, (S)-2,2'-dilt;(R)-2-(o-chlorophenyl)-2-hydroxyethoxygt;-1,1'-binaphthyl in tetrahydrofuran, Time= 0.5h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron Letters; vol. 38; nb. 15; (1997); p. 2709 - 2712 View in Reaxys With samarium diiodide, (R,R)-lt;PhCH(OH)CH2N(CH2Ph)CH2gt;2 in tetrahydrofuran, Time= 0.5h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Mikami, Koichi; Yamaoka, Makoto; Yoshida, Akihiro; Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Synlett; nb. 6; (1998); p. 607 - 608 View in Reaxys With samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, Time= 2h, T= -45 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron Letters; vol. 38; nb. 15; (1997); p. 2709 - 2712 View in Reaxys With samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, Time= 2h, T= -45 °C , enantioselectivity, various substrates and chiral proton source under different reaction conditions, Product distribution Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys With samarium diiodide, N,N'-dilt;(S)-hydroxy-2-phenylethylgt;-N,N'-di(benzyl)ethylenediamine in tetrahydrofuran, Time= 0.5h, Ambient temperature, Yield given, Yields of byproduct given. Title compound not separated from byproducts

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Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys With samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, Time= 2h, T= -45 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys With samarium diiodide, (R,S)-FDHPEB in tetrahydrofuran, Time= 2h, T= -45 °C , chiral protonation, Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Curran, Dennis P.; Tetrahedron; vol. 56; nb. 3; (2000); p.

351 - 356 View in Reaxys

O Cl

O

O

Rx-ID: 4675156 View in Reaxys 39/46 Yield

Conditions & References With samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, Time= 2h, T= -45 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron Letters; vol. 38; nb. 15; (1997); p. 2709 - 2712 View in Reaxys With samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, Time= 2h, T= -45 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys

O O O

O

O

Rx-ID: 4698630 View in Reaxys 40/46 Yield

Conditions & References With samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, Time= 2h, T= -45 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron Letters; vol. 38; nb. 15; (1997); p. 2709 - 2712 View in Reaxys With samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, Time= 2h, T= -45 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys

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22/24

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O Br

O

O

Rx-ID: 5146489 View in Reaxys 41/46 Yield

Conditions & References With samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, Time= 2h, T= -45 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys

O

O

Rx-ID: 16387652 View in Reaxys 42/46 Yield

Conditions & References Reaction Steps: 2 1: 19 percent / CrO3 / 0.5 h / 80 °C 2: SmI2, (R)-2,2'-di<(S)-2-hydroxy-2-phenylethoxy>-1,1'-binaphthyl / tetrahydrofuran / 2 h / -45 °C With chromium(VI) oxide, samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys Reaction Steps: 3 1: 48 percent HBr / CHCl3 / 0.5 h / Ambient temperature 2: Jones reagent / acetone / 1 h / 0 °C 3: SmI2, (R)-2,2'-di<(S)-2-hydroxy-2-phenylethoxy>-1,1'-binaphthyl / tetrahydrofuran / 2 h / -45 °C With jones reagent, samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl, hydrogen bromide in tetrahydrofuran, chloroform, acetone Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys Reaction Steps: 3 1: HCl 2: Jones reagent / acetone / 1 h / 0 °C 3: SmI2, (R)-2,2'-di<(S)-2-hydroxy-2-phenylethoxy>-1,1'-binaphthyl / tetrahydrofuran / 2 h / -45 °C With hydrogenchloride, jones reagent, samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, acetone Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys

HO

Br

O

Rx-ID: 16408186 View in Reaxys 43/46

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Yield

Conditions & References Reaction Steps: 2 1: Jones reagent / acetone / 1 h / 0 °C 2: SmI2, (R)-2,2'-di<(S)-2-hydroxy-2-phenylethoxy>-1,1'-binaphthyl / tetrahydrofuran / 2 h / -45 °C With jones reagent, samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, acetone Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys

HO

Cl

O

Rx-ID: 16408188 View in Reaxys 44/46 Yield

Conditions & References Reaction Steps: 2 1: Jones reagent / acetone / 1 h / 0 °C 2: SmI2, (R)-2,2'-di<(S)-2-hydroxy-2-phenylethoxy>-1,1'-binaphthyl / tetrahydrofuran / 2 h / -45 °C With jones reagent, samarium diiodide, (R)-2,2'-dilt;(S)-2-hydroxy-2-phenylethoxygt;-1,1'-binaphthyl in tetrahydrofuran, acetone Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Yamaoka, Makoto; Yoshida, Akihiro; Mikami, Koichi; Tetrahedron; vol. 55; nb. 15; (1999); p. 4595 - 4620 View in Reaxys

Si

O

O

O

Rx-ID: 5023240 View in Reaxys 45/46 Yield

Conditions & References Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Ishihara, Kazuaki; Nakamura, Hiroko; Nakamura, Shingo; Yamamoto, Hisashi; Journal of Organic Chemistry; vol. 63; nb. 19; (1998); p. 6444 - 6445 View in Reaxys

Si

O

O

Rx-ID: 4097796 View in Reaxys 46/46 Yield

Conditions & References With (S)-binaphthol, tin(IV) chloride in toluene, Time= 1h, T= -78 °C , Yield given Ishihara, Kazuaki; Kaneeda, Masanobu; Yamamoto, Hisashi; Journal of the American Chemical Society; vol.

116; nb. 24; (1994); p. 11179 - 11180 View in Reaxys

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