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1 Supporting Information Wiley-VCH Weinheim, Germany
2 Diphenylprolinol Silyl Ether in Enantioselective, Catalytic Tandem Michael-Henry Reaction for the Control of Four Stereocenters Yujiro Hayashi*, Tsubasa Okano, Seiji Aratake, Damien Hazerard Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo , Japan Typical procedure for the synthesis of (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (S)-2-Diphenyltrimethylsiloxymethylpyrrolidine (8.8 mg, mmol) was added to a mixture of 1-phenyl-2-nitroethylene (40.3 mg, 0.27 mmol) and glutaraldehyde solution (50% in water, 147 μl, 0.81 mmol) in THF (0.54 ml) at room temperature. The reaction mixture was stirred for 17 h at this temperature, the reaction was quenched by addition of 1 N hydrochloric acid for 3 min. Organic materials were extracted with ethyl acetate two times. The combined organic extracts were washed with brine five times, dried over anhydrous Na 2 SO 4 and concentrated in vacuo after filtration. Purification by neutral silica gel column chromatography (hexane : AcOEt = 2 : 1) gave (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (50.6 g, 0.20 mmol) in 88% yield as the diastereomeric mixture (5a:5b:5c:5d=75:8:8:9). Typical procedure for the synthesis of (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (large scale) (S)-2-Diphenyltrimethylsiloxymethylpyrrolidine (239 mg, 0.73 mmol) was added to a mixture of 1-phenyl-2-nitroethylene (5.5 g, 36.7 mmol) and glutaraldehyde solution (50% in water, 13.3 ml, 73.3 mmol) in THF (36.7 ml) at room temperature. The reaction mixture was stirred for 22 h at this temperature, the reaction was quenched by addition of 1 N hydrochloric acid for 3 min. Organic materials were extracted with ethyl acetate two times. The combined organic extracts were washed with brine five times, dried over anhydrous Na 2 SO 4 and concentrated in vacuo after filtration. Purification by neutral silica gel column chromatography (hexane : AcOEt = 2 : 1) gave (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (6.5 g, 26.0 mmol) in 92% yield as the diastereomeric mixture (5a:5b:5c:5d=73:8:7:12). Synthesis of (1S, 2S, 3S,4R)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (5a to 5b) (1R, 2S, 3S, 4R)-4-Hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (33.4 mg, mmol) was charged on preparative thin layer chromatography plate and it left for 5 h. After that, the TLC was developed by hexane and AcOEt (2:1) for 1 h, which afforded (1S, 2S, 3S,4R)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (31.3 mg, mmol) in 94% yield. Synthesis of (1S, 2S, 3S, 4S)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (5b to 5c) A solution of 1, 8-diazabicyclo[5.4.0]-undec-7-ene in methanol (0.05 M, 0.25 ml) was added to (1S, 2S, 3S,4R)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (31.3 mg, mmol) at room temperature. The reaction mixture was stirred for 20 h at this temperature, the reaction was quenched with ph 7.0 phosphate buffer solution. Organic materials were extracted with ethyl acetate two times. The combined organic extracts were washed with brine three times, dried over anhydrous Na 2 SO 4 and concentrated in vacuo after filtration. Purification by preparative thin layer chromatography (hexane : AcOEt = 1 : 1) gave (1S, 2S, 3S, 4S)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (25.9 mg, mmol) in 83% yield. Synthesis of (1S, 2S, 3S, 4S)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (5a to 5c) A solution of 1, 8-diazabicyclo[5.4.0]-undec-7-ene in methanol (0.05 M, 0.20 ml) was added to (1R, 2S, 3S, 4R)-4-Hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (24.8 mg, mmol) at room temperature. The reaction mixture was stirred for 20 h at this temperature, the reaction was quenched with ph 7.0 phosphate buffer solution. Organic materials were extracted with ethyl acetate two times. The combined organic extracts were washed with brine three times, dried over anhydrous Na 2 SO 4 and concentrated in vacuo after filtration. Purification by preparative thin layer chromatography (hexane : AcOEt = 1 : 1) gave (1S, 2S, 3S, 4S)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (19.8 mg, mmol) in 80% yield. (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (5a) 1 H NMR (CDCl 3, 400 MHz): δ (1H, m), (1H, m), (1H, m), (1H, m), 2.43 (1H, br-s), 3.19 (1H, t, J = 4.8 Hz), 4.04 (1H, dd, J = 12.2, 4.8 Hz), S1
3 4.60 (1H, br-s), 5.63 (1H, dd, J = 12.2, 2.4 Hz), (5H, m), 9.49 (1H, s); 13 C NMR (CDCl 3, 100 MHz): δ 18.4, 27.6, 40.7, 52.4, 67.9, 87.4, 127.6, 127.9, 128.9, 137.5, 202.4; IR (neat): ν , , , , , , , , , 756.9, cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 13 H 15 NNaO 4 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (25:1 hexane:2-propanol), 1.0 ml/min; major enantiomer tr = 46.9 min, minor enantiomer tr = 57.8 min. (1S, 2S, 3S,4R)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (5b) 1 H NMR (CDCl 3, 400 MHz): δ (2H, m), (1H, m), (1H, m), (2H, m), 3.92 (1H, t, J = 12.0 Hz), 4.58 (1H, br-s), 4.82 (1H, dd, J = 12.0, 2.4 Hz), NO (5H, m), 9.40 (1H, d, 2.4 Hz); 2 13 C NMR (CDCl 3, 100 MHz): δ 19.4, 30.2, 41.3, 54.0, 67.1, 92.7, 128.1, 128.3, 129.2, 136.6, 200.7; IR (neat): ν , , , , , , , , , , 758.9, cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 13 H 15 NNaO 4 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (20:1 hexane:2-propanol), 1.0 ml/min; major enantiomer tr = 22.4 min, minor enantiomer tr = 30.7 min. (1S, 2S, 3S, 4S)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (5c) 1 H NMR (CDCl 3, 400 MHz): δ (2H, m), (1H, m), (1H, m), (1H, m), 3.39 (1H, t, J = 11.6 Hz), 4.21 (1H, td, J = 10.8, 4.4 Hz), 4.62 (1H, dd, J = 11.6, 10.8 Hz), (5H, m), 9.35 (1H, d, 2.4 Hz); 13 C NMR (CDCl 3, 100 MHz): δ 23.9, 31.8, 47.5, 53.0, 71.7, 96.7, 127.8, 128.5, 129.3, 135.6, 200.6; IR (neat): ν , , , , , , , , 750.2, cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 13 H 15 NNaO 4 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (20:1 hexane:2-propanol), 1.0 ml/min; minor enantiomer tr = min, major enantiomer tr = min. (1R, 2S, 3S, 4S)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (5d) 1 H NMR (CDCl 3, 400 MHz): δ (2H, m), (1H, m), (2H, m), 3.12 (1H, t, J = 3.6 Hz), 3.55 (1H, dd, J = 12.0, 3.6 Hz), 4.19 (1H, m), 5.42 (1H, dd, J = 12.0, 9.2 Hz), (5H, m), 9.55 (1H, s); 13 C NMR (CDCl 3, 100 MHz): δ 22.9, 29.3, 47.2, 51.9, 73.0, 91.2, 128.0, 128.3, 128.9, 135.9, 201.6; IR (neat): ν , , , , , , , , , , cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 13 H 15 NNaO 4 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (20:1 hexane:2-propanol), 1.0 ml/min; major enantiomer tr = min, minor enantiomer tr = min, after conversion to (1S,2S,3S,4S)-4-hydroxy-3-nitro-2-phenylcyclohexanecarbaldehyde (5c). (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-(4-nitrophenyl)cyclohexanecarbaldehyde (Table 2, Entry 2) 1 H NMR (CDCl 3, 400 MHz): δ (1H, m), (1H, m), (1H, m), (1H, m), 2.41 (1H, br-s), 3.18 (1H, t, J = 4.8 Hz), 3.99 (1H, dd, J = 12.4, 4.8 Hz), 4.57 (1H, br-d, J = 2.8 Hz), 5.66 (1H, dd, J = 12.4, 2.8 Hz), 7.36 (2H, br-d, J = 8.0 Hz), 8.04 (2H, br-d, J = 8.0 Hz), 9.31 (1H, s); 13 C NMR (CDCl NO O 2 3, 100 MHz): δ 14.1, 27.6, 40.3, 52.7, 67.8, 86.5, 123.9, 129.0, 145.8, 2 N 147.1, 201.0; IR (neat): ν , , , , , , , , , , 878.4, 753.1, cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 13 H 14 N 2 NaO 6 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (10:1 hexane:2-propanol), 1.0 ml/min; minor enantiomer tr = 65.0 min, major enantiomer tr = 72.4 min. (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-(4-bromophenyl)cyclohexanecarbaldehyde (Table 2, Entry 3) 1 H NMR (CDCl 3, 400 MHz): δ 1.63 (1H, tdd, J = 14.4, 4.8, 2.4 Hz), 1.82 (1H, ddt, J = 14.4, 3.6, 2.4 Hz), (1H, m), 2.24 (1H, tdd, J = 14.4, 6.0, 3.6 Hz), 2.35 (1H, br-s), 3.14 (1H, t, J = 4.8 Hz), 3.91(1H, dd, J = 12.4, 4.8 Hz), 4.56 (1H, br-d, J = 3.2 Hz), 5.60 (1H, dd, 12.4, 2.4 Hz), 7.10 (2H, br-d, J = 8.4 Hz), 7.36 (2H, br-d, J = 8.4 Hz), 9.41 (1H, s); 13 NO C NMR (CDCl 2 3, 100 MHz): δ 16.1, 25.3, 38.1, 50.4, 65.7, 84.9, , 127.6, 129.8, Br 134.7, 199.7; IR (neat): ν , , , , , , , , , cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 13 H 14 BrNNaO 4 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (30:1 hexane:2-propanol), 1.0 ml/min; minor enantiomer tr = 90.4 min, major enantiomer tr = 99.4 min. S2
4 (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-(2-bromophenyl)cyclohexanecarbaldehyde (Table 2, Entry 4) 1 H NMR (CDCl 3, 400 MHz): δ 1.70 (1H, tdd, J = 14.4, 4.4, 2.4 Hz), 1.91 (1H, m), 2.01 (1H, dq, J = 14.4, 2.4 Hz), 2.32 (1H, tdd, J = 14.4, 5.6, 4.4 Hz), 3.44 (1H, t, J = 4.4 Hz), 4.46 (1H,dd, J = 12.4, 4.4 Hz), 4.64 (1H, dd, J = 5.6, 2.4 Hz), 5.70 (1H, dd, J = 12.4, 2.4 Hz), 7.08 (1H, td, 7.6, 1.6 Hz), 7.22 (1H, td, J = 7.6, 1.6 Hz), 7.32 (1H, dd, J = 7.6, 1.6 Hz), 7.56 (1H, dd, J = 7.6, 1.6 Hz), 9.44 (1H, s); Br 13 C NMR (CDCl 3, 100 MHz): δ 18.0, 22.7, 39.6, 49.3, 68.1, 87.0, 127.6, 128.2, 129.0, 130.9, 133.7, 136.2, 201.8; IR (neat): ν , , , , , , , , , 846.6, 749.7, cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 13 H 14 BrNNaO 4 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak AD-H column (10:1 hexane:2-propanol), 1.0 ml/min; major enantiomer tr = 22.6 min, minor enantiomer tr = 34.2 min, after conversion to (1S,2S,3S,4S)-4-hydroxy-3-nitro-2-(2-bromophenyl)cyclohexanecarbaldehyde. (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-(2-naphtyl)cyclohexanecarbaldehyde (Table 2, Entry 5) 1 H NMR (CDCl 3, 400 MHz): δ (1H, m), (1H, m), (1H, m), (1H, m), 2.44 (1H, br-s), 3.30 (1H, br-t, J = 4.8 Hz), 4.21 (1H, dd, J = 12.4, 4.8 Hz), 4.66 (1H, br-s), 5.77 (1H, dd, J = 12.4, 2.4 Hz), (3H, m), 7.70 (1H, br-s), (3H, m), 9.50 (1H, s); 13 C NMR (CDCl 3, 100 MHz): δ 18.4, 27.6, 40.8, 52.3, 68.0, 87.5, 126.0, 126.2, 126.4, 126.6, 127.6, 127.9, 128.7, 132.6, 133.2, 135.0, 202.5; IR (neat): ν , , , , , , , 896.7, 864.9, 813.8, 751.1, cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 17 H 17 NNaO 4 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak AS-H column (10:1 hexane:2-propanol), 1.0 ml/min; minor enantiomer tr = 13.7 min, major enantiomer tr = 17.1 min. (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-(4-methoxyphenyl)cyclohexanecarbaldehyde (Table 2, Entry 6) 1 H NMR (CDCl 3, 400 MHz): δ (1H, m), (1H, m), (1H, m), (1H, m), 2.46 (1H, br-s), 3.16 (1H, t, J = 4.8 Hz), 3.75 (3H, s), 3.98 (1H, dd, J = 12.4, 4.8 Hz), 4.57 (1H, br-s), 5.57 (1H, dd, J = 12.4, 2.4 Hz), 6.81 (2H, br-d, J = 8.4 Hz), 7.17(2H, br-d, J = 8.4 Hz), 9.52 (1H, s); 13 MeO C NMR (CDCl 3, 100 MHz): δ 18.4, 27.5, 40.2, 52.5, 55.2, 67.9, 87.8, 114.2, 129.1, 129.3, 158.9, 202.6; IR (neat): ν , , , , , , , , , , , , 864.9, cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 14 H 17 NNaO 4 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (10:1 hexane:2-propanol), 1.0 ml/min; major enantiomer tr = 26.7 min, minor enantiomer tr = 33.7 min. (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-(3, 4-methylendioxyphenyl)cyclohexanecarbaldehyde (Table 2, Entry 7) 1 H NMR (CDCl 3, 400 MHz): δ (1H, m), (1H, m), (1H, m), (1H, m), 2.34 (1H, br-s), 3.12 (1H, t, J = 5.6 Hz), 3.89 (1H, dd, J = 12.4, 4.8 Hz), 4.53 (1H, br-s), 5.51 (1H, dd, J = 12.8, 2.4 Hz), 5.86 (2H, br-s), 6.66 (2H, br-s), 6.71 (1H, O br-s), 9.49 (1H, s); O 13 C NMR (CDCl 3, 100 MHz): δ 18.4, 27.5, 40.6, 52.5, 67.9, 87.7, 101.2, 108.5, 121.2, 128.3, 131.1, 147.0, 148.0, 202.5; IR (neat): ν , , , , , , , , 934.3, cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 14 H 15 NNaO 6 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (10:1 hexane:2-propanol), 1.0 ml/min; major enantiomer tr = 32.1 min, minor enantiomer tr = 36.7 min. (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-(2-furyl)cyclohexanecarbaldehyde (Table 2, Entry 8) 1 H NMR (CDCl 3, 400 MHz): δ (1H, m), (2H, m), (1H, m), 2.43 (1H, br-d, J = 4.0 Hz), 3.21 (1H, br-s), 4.22 (1H, dd, J = 11.2, 5.6 Hz), 4.51 (1H, br-s), 5.27 (1H, dd, J = 11.2, 2.4 Hz), 6.14 (1H, d, J = 3.2), 6.20 (1H, dd, J = 3.2, 2.0 Hz), 7.25 (1H, d, J = 2.0 Hz), 9.58 (1H, s); 13 C NMR (CDCl O 3, 100 MHz): δ 17.9, 29.7, 35.0, 49.8, 67.5, 87.1, 107.6, 110.6, 142.0, 151.0, 201.8; IR (neat): ν , , , , , , , , , 911.2, 739.6, cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 11 H 13 NNaO 5 ]: , found: ; S3
5 Enantiomeric excess was determined by HPLC with a Chiralpak IA column (10:1 hexane:2-propanol), 1.0 ml/min; major enantiomer tr = 40.9 min, minor enantiomer tr = 51.9 min. (1R, 2S, 3S, 4R)-4-hydroxy-3-nitro-2-(1-tert-butoxycarbonylindol-3-yl)cyclohexanecarbaldehyde (Table 2, Entry 9) 1 H NMR (CDCl 3, 400 MHz): δ 1.64 (9H, s), (1H, m), (1H, m), (1H, m), (1H, m), 2.49 (1H, br-q, J = 1.6 Hz), 3.31 (1H, br-s), 4.33 (1H, dd, J = 12.0, 4.8 Hz), 4.57 (1H, br-s), 5.57 (1H, dd, J = 12.0, 2.4 Hz), (2H, m), 7.43 (1H, s), 7.58 (1H, br-d, 7.6 Hz), 8.19 (1H, d, 7.6 Hz), 9.54 (1H, s); 13 C NMR (CDCl 3, 100 MHz): δ 18.0, 27.5, 28.2, 31.7, 49.6, 67.6, 84.1, 87.9, , 116.5, 118.3, 122.8, 123.5, 124.9, 129.3, 135.2, 149.4, 202.3; IR (neat): ν , , , , , , , , , , , , , , , 762.7cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 20 H 24 N 2 NaO 6 ]: , found: ; N Boc Enantiomeric excess was determined by HPLC with a Chiralpak IA column (30:1 hexane:2-propanol), 1.0 ml/min; major enantiomer tr = 25.2 min, minor enantiomer tr = 27.8 min. (1R, 2R, 3S, 4R)- 4-hydroxy-3-nitro-2-styrylcyclohexanecarbaldehyde (Table 2, Entry 10) 1 H NMR (CDCl 3, 400 MHz): δ 1.45 (1H, br-t, J = 14.0 Hz), (2H, m), (1H, m), 2.88 (1H, br-s), 3.01 (1H, br-s), (1H, m), 4.39 (1H, br-s), 5.10 (1H, dd, J = 11.2, 2.4 Hz), 6.27 (1H, dd, J = 14.4, 8.4 Hz), 6.48 (1H, d, J = 14.4 Hz), (5H, m), 9.61 (1H, s); 13 C NMR (CDCl 3, 100 MHz): δ 17.6, 27.4, 39.7, 51.8, 66.6, 88.4, 124.9, 126.5, 128.0, 128.6, 134.8, 136.2, 201.8; IR (neat): ν , , , , , , , , , 971.0, 748.3, cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 15 H 17 NNaO 4 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (10:1 hexane:2-propanol), 1.0 ml/min; minor enantiomer tr = 12.2 min, major enantiomer tr = 14.9 min. (1R, 2R, 3S, 4R)-4-hydroxy-3-nitro-2-cyclohexylcyclohexanecarbaldehyde (Table 2, Entry 11) 1 H NMR (CDCl 3, 400 MHz): δ (1H, m), (4H, m), (1H, m), (7H, m), (1H, m), (1H, m), 2.69 (1H, quint, J = 4.8 Hz), 2.86 (1H, br-s), 2.97 (1H, br-d, J = 3.6 Hz), 4.32 (1H, q, J = 2.4 Hz), 5.28 (1H, dd, J = 10.8, 2.4 Hz), 9.84 (1H, br-s); NO 13 2 C NMR (CDCl 3, 100 MHz): δ 19.1, 26.2, 26.6, 26.8, 27.4, 31.4, 31.8, 38.4, 41.5, 47.3, 67.6, 88.1, 202.7; IR (neat): ν , , , , , , , , , , , , cm -1 ; HRMS (ESI) : [M+Na] calcd for [C 13 H 21 NNaO 4 ]: , found: ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (30:1 hexane:2-propanol), 1.0 ml/min; minor enantiomer tr = 27.2 min, major enantiomer tr = 31.0 min. Determination of absolute configuration. The absolute configuration was determined by Mosher s MPTA method 1 from 7c. Br 7c + + Ph OMe Cl CF 3 O (R) MeO Ph Cl CF 3 O (S) NEt 3, DMAP CH 2 Cl 2 quant. NEt 3, DMAP CH 2 Cl 2 70 % Br Br O O CF 3 MeO Ph (S)-MPTA ester O O CF 3 Ph OMe (R)-MPTA ester S4
6 (1S, 2S, 3S, 4S) 2-(4-Bromo-phenyl)-4-hydroxy-3-nitro-cyclohexanecarbaldehyde 7c According to typical procedure 7c was prepared in 52 % yield from glutaraldehyde and 1-Bromo-4-(2-nitro-vinyl)-benzene after racemization with DBU (5 % mol) in Me. 1 H (CDCl 3, 400 MHz) δ (2H, m), (1H, m), 2.27 (1H, s br), (1H, m), (1H, m), 3.41 (1H, t, J=11.6 Hz), (1H, m), 4.57 (1H, dd, J=11.6 Hz, J=9.6), 7.09 (2H, d, J=8.8 Hz), 7.46 (2H, d, J=8,6 Hz), 9.39 (1H, d, J=2Hz, 1H) 13 C (CDCl 3, 100 MHz) δ 23.9, 31.7, 46.7, 52.9, 71.5, 96.4, 122.4, 129.5, 132.4, 134.9, IR (neat) 3421, 2934, 2867, 2731, 1724, 1661, 1591, 1555, 1489, 1455, 1412, 1376, 1272, 1212, 1108, 1073, 1011, 911, 817, 734, 664, 553, 420. HRMS (ESI) : [M+Na] calcd for [C 13 H 14 NO 4 Na]: , found: Ee = 93 % (determined by HPLC with a Chiralpak IA column (10:1 hexane:2-propanol), 1.0 ml/min; major enantiomer tr = 58.8 min, minor enantiomer tr = 68.1 min. Synthesis of (R)-MPTA ester : 7c (4.2 mg, mmol) was dissolved in dichloromethane (0,5 ml). Then Et 3 N (5 μl, mmol), DMAP (4.1 mg, mmol) and 1 drop of (S) 3,3,3-Trifluoro-2-methoxy-2-phenyl-propionyl chloride were successively added. The mixture was stirred 3.5 h at room temperature. Then the mixture was concentrated and purified by preparative TLC to give 4.7 mg (70 % yield) of (R)-MPTA ester. 1 H (CDCl 3, 400 MHz) δ (2H, m), (1H, m), (1H, m), 2.80 (1H, t, J=10.8 Hz), 3.44 (1H, t, J=11.6 Hz), 3.46 (3H, s), 4.75 (1H, t, J=11.2 Hz), (1H, m), 7.06 (2H, d, J=8,4 Hz), (5H, m), 7.45 (2H, d, J=8,4 Hz), 9.39 (1H, d, J=2Hz) Synthesis of (S)-MPTA ester (R)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionyl chloride was prepared from (S)-3,3,3-Trifluoro-2-methoxy-2- phenyl-propionic acid according to literature 2 : To a solution of the acid (15 mg, mmol) in hexane (2.5 ml) was added DMF (4.5 mg, mmol) and oxalic chloride (25 μl, 0.29 mmol). The mixture was stirred 1.5 h at room temperature and concentrated in vaccuo. To the crude mixture was added 7c (4.4 mg, mmol), dichloromethane (0.5 ml), Et 3 N (5 μl, mmol) and DMAP (4.4 mg, mmol). The mixture was stirred at room temperature 3,5 h, then it was concentrated in vaccuo to give after preparative TLC (S)-MPTA ester with quantitative yield. 1 H (CDCl 3, 400 MHz) δ (1H, m), (1H, m), (1H, m), (1H, m), (1H, m), 3.43 (3H, s), 3.46 (1H, t, J=10.4 Hz), 4.76 (1H, dd, J=11.6 Hz, 10,4 Hz), 5.55 (1H, td, J= 10.8 Hz, 4.8 Hz), 7.06 (2H, d, J=8,4 Hz), (5H, m), 7.46 (2H, d, J=8,4 Hz), 9.38 (1H, d, J=2Hz) Representation of MPTA ester with Δδ and determination of absolute configuration according to Kakisawa model 1 Br S S S S OMPTA -0.04H -0.01H H +0 H Br H H H H OMPTA Δδ<0 OMPTA C Δδ>0 H Δδ = δ((s)-mpta) δ((r)-mpta) Represention of MPTA ester with Δδ (left)for some protons and Kakisawa model (rigth) The scheme above show clearly that all the protons in the right side of MPTA plan have positive values while these in the left have negative values. According to Kakisawa, 1 the absolute configuration of hydroxyl group in 7c is (S). The relative configuration is determined by coupling constants. S5
7 References 1) I. Ohtani, T. Kusumi, Y. Kashman, H. Kakisawa, J. Am. Chem. Soc. 1991, 113, ) D.E. Ward, C. K. Rhee, Tetrahedron Letters 1991, 32, S6
8 S7
9 S8
10 S9
11 S10
12 S11
13 S12
14 S13
15 S14
16 S15
17 S16
18 S17
19 O 2 N S18
20 O 2 N S19
21 O 2 N S20
22 Br S21
23 Br S22
24 Br S23
25 Br S24
26 Br S25
27 Br S26
28 S27
29 S28
30 S29
31 MeO S30
32 MeO S31
33 MeO S32
34 O O S33
35 O O S34
36 O O S35
37 O S36
38 O S37
39 O S38
40 N Boc S39
41 N Boc S40
42 N Boc S41
43 S42
44 S43
45 S44
46 S45
47 S46
48 S47
49 Br S48
50 Br S49
51 Br S50
52 S51 (R) and (S)- MPTA esters of 7c
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