2396
S. Fu et al. / Tetrahedron: Asymmetry 20 (2009) 2390–2396
2928, 1692, 1460, 825. Enantiomeric excess was determined by
HPLC with a Chiralpak AD column (hexane/2-propanol = 90/10),
21 °C, 220 nm, 0.5 mL/min; major enantiomer tR = 43.1 min and
minor enantiomer tR = 35.5 min.
Acknowledgment
Authors are grateful to Southwest University of China for finan-
cial support.
4.2.10. (2S,10R)-2-(Hydroxyl (2-chlorophenyl)methyl)
cyclohexan-1-one 7i
References
>99% ee. 1H NMR (300 MHz, CDCl3) 1.53–1.84 (m, 5H), 2.05–
2.13 (m, 1H), 2.31–2.39 (m, 1H), 2.46–2.49 (m, 1H), 2.65–2.71
(m, 1H), 3.88 (s, 1H), 5.35 (d, J = 8.0 Hz, 1H), 7.20–7.34 (m, 3H),
7.56 (d, J = 8.4 Hz, 1H); Enantiomeric excess was determined by
HPLC with Chiralcel OD-H (hexane/i-PrOH = 95/5), 21 °C, 220 nm,
flow rate 1.0 mL/min, major enantiomer tR = 10.5 min and minor
enantiomer tR = 13.7 min.
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4.2.11. (2S,10R)-2-(Hydroxyl (3-chlorophenyl) methyl)
cyclohexan-1-one 7j
99% ee. 1H NMR (300 MHz, CDCl3) 1.31–2.08 (m, 6H), 2.30–2.45
(m, 3H), 4.80 (d, J = 8.8 Hz, 1H), 7.20–7.29 (m, 3H, Ar), 7.37 (s, 1H,
Ar); Enantiomeric excess was determined by HPLC with Chiralcel
OD-H (hexane/i-PrOH = 96/4), 21 °C, 220 nm, flow rate 1.0 mL/
min, major enantiomer tR = 14.8 min and minor enantiomer tR =
21.2 min.
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4.2.12. (2S, 10R)-2-(Hydroxy (phenyl) methyl) cyclohexan-1-one
7k
½
a 2D2
ꢂ
¼ þ23:3 (c 1.55, CHCl3), 98% ee. 1H NMR (300 MHz, CDCl3):
d 7.50–7.24 (5H, m), 4.80 (d, 1H, J = 9.0 Hz), 4.00 (m, 1H), 2.70–2.56
(m, 1H), 2.55–2.44 (m, 1H), 2.34 (td, 1H, J = 12.3, 5.4 Hz), 2.16–2.03
(m, 1H), 1.87–1.73 (m, 1H), 1.72–1.50 (m, 3H), 1.40–1.22 (m, 1H).
IR (film, cmꢁ1): 3508, 2932, 1697, 1451, 702. Enantiomeric excess
was determined by HPLC with a Chiralpak OD-H column (hexane/
2-propanol = 90/10), 20 °C, 220 nm, 0.5 mL/min; major enantiomer
tR = 19.6 min and minor enantiomer tR = 30.6 min.
4.2.13. (2S, 10R)-2-(Hydroxy(2-nitrophenyl)methyl)
cyclopentan-1-one 7l
Anti-isomer: 96% ee. 1H NMR (300 MHz, CDCl3): 1.70–2.03 (m,
4H), 2.19–2.38 (m, 2H), 2.68 (d, J = 7.6 Hz, 1H), 2.90 (br, 1H), 5.21
(d, J = 7.2 Hz, 1H), 7.44 (t, J = 8.0 Hz, 1H, Ar–H), 7.66 (t, J = 8.0 Hz,
1H, Ar–H), 7.89 (d, J = 8.0 Hz, 1H), 8.00 (dd, J = 8.0, 0.8 Hz, 1H);
Enantiomeric excess was determined by HPLC with a Chiralpak
OD-H column (hexane/2-propanol = 95/5), 20 °C, 254 nm, 1.0 mL/
min; major enantiomer tR = 27.4 min, minor enantiomer tR =
22.9 min, syn-isomer: 82% ee. Enantiomeric excess was deter-
mined by HPLC with a Chiralpak OD-H column (hexane/2-propa-
nol = 95/5), 20 °C, 254 nm, 1.0 mL/min; major enantiomer tR =
20.3 min and minor enantiomer tR = 17.2 min.
4.2.14. (2S, 10R)-2-(Hydroxy-(4-nitrophenyl) methyl)
cyclopentan-1-one 7m
½
a 2D2
ꢂ
¼ ꢁ30:6 (c 0.56, CHCl3), anti-isomer: >99% ee. 1H NMR
11. (a) Berkessel, A.; Koch, B.; Lex, J. Adv. Synth. Catal. 2004, 346, 1141–1146; (b)
Cobb, A. J. A.; Shaw, D. M.; Longbottom, D. A.; Gold, J. B.; Ley, S. V. Org. Biomol.
Chem. 2005, 3, 84–96; (c) Gandhi, S.; Singh, V. K. J. Org. Chem. 2008, 73, 9411–
9416.
12. (a) Lindstrom, U. M.; Andersson, F. Angew. Chem., Int. Ed. 2006, 45, 548–551; (b)
Otto, S.; Engberts, J. B. F. N. Org. Biomol. Chem. 2003, 1, 2809–2820.
13. (a) Maya, V.; Raj, M.; Singh, V. K. Org. Lett. 2007, 9, 2593–2595.
14. Ohtake, H.; Imada, Y.; Murahashi, S. Bull. Chem. Soc. Jpn. 1999, 72, 2737–
2754.
(300 MHz, CDCl3): d 8.21 (d, 2H, J = 8.7 Hz), 7.54 (d, 2H, J = 9.0 Hz),
4.85 (d, 1H, J = 9.0 Hz), 4.74 (s, 1H), 2.54–2.18 (m, 3H), 2.08–1.95
(m, 1H), 1.81–1.48 (m, 3H). IR (film, cmꢁ1): 3442, 2966, 1737,
1604, 1519, 1347, 857 cmꢁ1. Enantiomeric excess was determined
by HPLC with a Chiralpak AD column (hexane/2-propanol = 95/5),
20 °C, 254 nm, 1.0 mL/min; major enantiomer tR = 59.8 min, minor
enantiomer tR = 56.8 min. syn-isomer: 69% ee. Enantiomeric excess
was determined by HPLC with a Chiralpak AD column (hexane/2-
propanol = 95/5), 20 °C, 254 nm, 1.0 mL/min; major enantiomer
tR = 31.1 min and minor enantiomer tR = 44.7 min.