Supporting Information Enantioselective reduction of prochiral ketones ...
Supporting Information
Enantioselective reduction of prochiral ketones with NaBH4/Me2SO4/(S)-Me-CBS Yuhan Zhou*, Guchao Gao, Yuming Song, Jingping Qu* (State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024, P.R. China) Address correspondence to Yuhan Zhou and Jingping Qu, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024, P. R. China. Email: [email protected] (Y. Zhou); [email protected] (J. Qu).
Contents
Spectroscopic and characterization data of the alcohols
S2
1
S4
H NMR spectra of the alcohols
HPLC chromatograms of the racemic and chiral alcohols
S12
S1
Spectroscopic and characterization data of the alcohols 1-Phenylethanol:[1] Colorless liquid, yield 99%, 96% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 95/5; flow rate: 0.5 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3): δ 7.37-7.24 (m, 5H, PhH), 4.87 (q, J ＝ 6.4 Hz, 1H, CH), 2.08 (s, 1H, OH), 1.48 (d, J ＝ 6.4 Hz, 3H, CH3). 1-Phenylpropan-1-ol:[2] Colorless liquid, yield 99%, 98% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 98/2; flow rate: 0.5 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.37-7.25 (m, 5H, Ph-H), 4.58 (t, J ＝ 6.4 Hz, 1H, CH), 2.15 (s, 1H, OH), 1.86-1.71 (m, 2H, CH2), 0.91 (t, J ＝ 7.2 Hz, 3H, CH3). 2-Chloro-1-phenylethanol:[1] Colorless liquid, yield 97%, 96% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 98/2; flow rate: 0.6 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.39-7.31 (m, 5H, PhH), 4.90 (m, 1H, CH), 3.77-3.62 (m, 2H, CH2), 2.65 (d, J ＝ 2.8 Hz, 1H, OH). 2-Bromo-1-phenylethanol:[1] Colorless liquid, yield 98%, 95% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 98/2; flow rate: 0.6 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.39-7.30 (m, 5H, PhH), 4.93 (m, 1H, CH), 3.67-3.52 (m, 2H, CH2), 2.62 (m, 1H, OH). 1-(4-Chlorophenyl)ethanol:[3] Colorless liquid, yield 90%, 97% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 99/1; flow rate: 0.5 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.31 (m, 4H, PhH), 4.88 (m, 1H, CH), 1.91 (s, 1H, OH), 1.47 (d，J ＝ 6.4 Hz, 3H, CH3). 1-(4-Bromophenyl)ethanol:[3] Colorless liquid, yield 80%, 97% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 99/1; flow rate: 0.5 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.47 (d, 2H, J ＝ 8.4 Hz, PhH), 7.25 (d, 2H, J ＝ 8.4 Hz, PhH), 4.86 (q, J ＝ 6.4 Hz, 1H, CH), 1.85 (s, 1H, OH), 1.47 (d, J ＝ 6.4 Hz, 3H, CH3). 1-(Naphthalen-2-yl)ethanol:[1] Colorless liquid, yield 94%, 99% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 98/2; flow rate: 0.6 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.81-7.22 (m, 7H, Ar-H), 5.02 (q, J ＝ 6.4 Hz, 1H, CH), 2.10 (s, 1H, OH), 1.55 (d, J ＝ 6.4 Hz, 3H, CH3).
S2
3-Chloro-1-phenylpropan-1-ol:[4] Colorless liquid, yield 95%, 93% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 97/3; flow rate: 0.5 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.37-7.28 (m, 5H, PhH), 4.94 (m, 1H, CH), 3.77-3.53 (m, 2H, CH2-Cl), 2.28-2.01 (m, 2H, CH2), 2.00 (s, 1H, OH).
REFERENCES 1. Xiao, J.; Wong, Z. Z.; Lu, Y. P.; Loh, T. P. Adv. Synth. Catal. 2010, 352, 1107-1112. 2. Wu, X.-F.; Min, C.; Nyamzundui, E.; Zhou, H.-B.; Dong, C. Tetrahedron: Asymmetry 2011, 22, 1640-1643. 3. Stepanenko, V.; Jesús, M. D.; Correa, W.; Guzmán, I.; Vázquez, C.; Cruz, W.; Ortiz-Marciales, M.; Barnes, C. L. Tetrahedron Lett. 2007, 48, 5799-5802. 4. Mahale, R. D.; Chaskar, S. P.; Patil, K. E.; Maikap, G. C.; Gurjar, M. K. Org. Process. Res. Dev. 2012, 16, 710-713.
S3
1
H NMR spectra of the alcohols
S4
OH Et
S5
S6
S7
S8
S9
S10
S11
HPLC chromatograms of the racemic and chiral alcohols 1-Phenylethanol
S12
1-Phenylpropan-1-ol
S13
2-Chloro-1-phenylethanol
S14
2-Bromo-1-phenylethanol
S15
1-(4-Chlorophenyl)ethanol
S16
1-(4-Bromophenyl)ethanol
S17
1-(Naphthalen-2-yl)ethanol
S18
3-Chloro-1-phenylpropan-1-ol
S19
Enantioselective reduction of prochiral ketones with NaBH4/Me2SO4/(S)-Me-CBS Yuhan Zhou*, Guchao Gao, Yuming Song, Jingping Qu* (State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024, P.R. China) Address correspondence to Yuhan Zhou and Jingping Qu, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024, P. R. China. Email: [email protected] (Y. Zhou); [email protected] (J. Qu).
Contents
Spectroscopic and characterization data of the alcohols
S2
1
S4
H NMR spectra of the alcohols
HPLC chromatograms of the racemic and chiral alcohols
S12
S1
Spectroscopic and characterization data of the alcohols 1-Phenylethanol:[1] Colorless liquid, yield 99%, 96% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 95/5; flow rate: 0.5 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3): δ 7.37-7.24 (m, 5H, PhH), 4.87 (q, J ＝ 6.4 Hz, 1H, CH), 2.08 (s, 1H, OH), 1.48 (d, J ＝ 6.4 Hz, 3H, CH3). 1-Phenylpropan-1-ol:[2] Colorless liquid, yield 99%, 98% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 98/2; flow rate: 0.5 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.37-7.25 (m, 5H, Ph-H), 4.58 (t, J ＝ 6.4 Hz, 1H, CH), 2.15 (s, 1H, OH), 1.86-1.71 (m, 2H, CH2), 0.91 (t, J ＝ 7.2 Hz, 3H, CH3). 2-Chloro-1-phenylethanol:[1] Colorless liquid, yield 97%, 96% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 98/2; flow rate: 0.6 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.39-7.31 (m, 5H, PhH), 4.90 (m, 1H, CH), 3.77-3.62 (m, 2H, CH2), 2.65 (d, J ＝ 2.8 Hz, 1H, OH). 2-Bromo-1-phenylethanol:[1] Colorless liquid, yield 98%, 95% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 98/2; flow rate: 0.6 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.39-7.30 (m, 5H, PhH), 4.93 (m, 1H, CH), 3.67-3.52 (m, 2H, CH2), 2.62 (m, 1H, OH). 1-(4-Chlorophenyl)ethanol:[3] Colorless liquid, yield 90%, 97% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 99/1; flow rate: 0.5 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.31 (m, 4H, PhH), 4.88 (m, 1H, CH), 1.91 (s, 1H, OH), 1.47 (d，J ＝ 6.4 Hz, 3H, CH3). 1-(4-Bromophenyl)ethanol:[3] Colorless liquid, yield 80%, 97% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 99/1; flow rate: 0.5 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.47 (d, 2H, J ＝ 8.4 Hz, PhH), 7.25 (d, 2H, J ＝ 8.4 Hz, PhH), 4.86 (q, J ＝ 6.4 Hz, 1H, CH), 1.85 (s, 1H, OH), 1.47 (d, J ＝ 6.4 Hz, 3H, CH3). 1-(Naphthalen-2-yl)ethanol:[1] Colorless liquid, yield 94%, 99% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 98/2; flow rate: 0.6 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.81-7.22 (m, 7H, Ar-H), 5.02 (q, J ＝ 6.4 Hz, 1H, CH), 2.10 (s, 1H, OH), 1.55 (d, J ＝ 6.4 Hz, 3H, CH3).
S2
3-Chloro-1-phenylpropan-1-ol:[4] Colorless liquid, yield 95%, 93% ee. The enantiomeric excess was determined by HPLC with a chiral column (Daicel OD; eluent: n-hexane/2-propanol = 97/3; flow rate: 0.5 mL/min; UV detector: 254 nm). 1H NMR (400 MHz, CDCl3) δ: 7.37-7.28 (m, 5H, PhH), 4.94 (m, 1H, CH), 3.77-3.53 (m, 2H, CH2-Cl), 2.28-2.01 (m, 2H, CH2), 2.00 (s, 1H, OH).
REFERENCES 1. Xiao, J.; Wong, Z. Z.; Lu, Y. P.; Loh, T. P. Adv. Synth. Catal. 2010, 352, 1107-1112. 2. Wu, X.-F.; Min, C.; Nyamzundui, E.; Zhou, H.-B.; Dong, C. Tetrahedron: Asymmetry 2011, 22, 1640-1643. 3. Stepanenko, V.; Jesús, M. D.; Correa, W.; Guzmán, I.; Vázquez, C.; Cruz, W.; Ortiz-Marciales, M.; Barnes, C. L. Tetrahedron Lett. 2007, 48, 5799-5802. 4. Mahale, R. D.; Chaskar, S. P.; Patil, K. E.; Maikap, G. C.; Gurjar, M. K. Org. Process. Res. Dev. 2012, 16, 710-713.
S3
1
H NMR spectra of the alcohols
S4
OH Et
S5
S6
S7
S8
S9
S10
S11
HPLC chromatograms of the racemic and chiral alcohols 1-Phenylethanol
S12
1-Phenylpropan-1-ol
S13
2-Chloro-1-phenylethanol
S14
2-Bromo-1-phenylethanol
S15
1-(4-Chlorophenyl)ethanol
S16
1-(4-Bromophenyl)ethanol
S17
1-(Naphthalen-2-yl)ethanol
S18
3-Chloro-1-phenylpropan-1-ol
S19
