L. M. Le6y et al. / Tetrahedron: Asymmetry 14 (2003) 2053–2058
2057
4.3.7. Ethyl (1S,2R)-2-acetoxycyclopentanecarboxylate,
(1S,2R)-7. Colourless oil. Yield 70%. [h]2D0 −8.0 (c 0.8,
CHCl3) >99% e.e. GC conditions: 100°C 15 min, 100–
170°C, 1°C/min, tR (1R,2S) 36.7 min and tR (S,R) 37.5
4.3.12. Methyl (1R,2R)-2-acetoxycycloheptanecarboxyl-
ate, (1R,2R)-12. Colourless oil. Yield 90%. [h]2D0 −13.4
(c 2.4, CHCl3) >99% e.e. GC conditions: 100°C isother-
mic, tR (1S,2S) 134.0 min and tR (1R,2R) 137.6 min. 1H
NMR l 1.4–1.8 (m, 13H), 2.6 (dt, 1H, J=3.5 and 9.0
Hz), 3.6 (s, 3H), 5.10 (ddd, 1H, J=3.8, 9.1 and 10.8
Hz) ppm. 13C NMR l 21.2 (CH3), 22.4 (CH2), 26.4
(CH2), 27.5 (CH2), 28.2 (CH2), 32.6 (CH2), 50.8 (CH or
CH3), 51.8 (CH or CH3), 75.6 (CH), 170.0 (CO), 174.8
(CO) ppm. ESIMS m/z 253 [(M+K)+, 5%], [(M+Na)+,
20%], 201 [(M+H)+, 100%]. IR (film) 1739 (CO) cm−1.
1
min. H NMR l 1.23 (t, 3H, J=7.2 Hz), 1.5–2.4 (m,
9H), 2.9 (ddd, 1H, J=5.8, 8.2 and 9.4 Hz), 4.1 (m, 2H),
5.42 (ddd, H, J=2.6, 5.4 and 5.3 Hz) ppm. 13C NMR
l 14.3 (CH3), 21.1 (CH3), 22.0 (CH2), 25.7 (CH2), 32.3
(CH2), 48.6 (CH), 60.4 (CH2), 76.6 (CH), 170.3 (CO),
171.9 (CO) ppm. ESIMS m/z 223 [(M+Na)+, 100%],
201 [(M+H)+, 20%]. IR (film) 1739 (CO) cm−1.
4.3.13. Ethyl (1R,2S)-2-hydroxycycloheptanecarboxyl-
ate, (1R,2S)-13. [h]D20 +48.7 (c 0.9, CHCl3) >99% e.e.
Lit.2b [h]D20 +37.0 (c 1.0, CHCl3) 94% e.e. The product
exhibited physical properties fully in agreement with the
4.3.8. Ethyl (1R,2R)-2-acetoxycyclopentanecarboxylate,
(1R,2R)-8. Colourless oil. Yield 81%. [h]2D0 −53.0 (c 1.3,
CHCl3) >99% e.e. HPLC conditions: hexane/propan-2-
ol, 96.5:3.5, 0.6 mL/min, tR (1S,2S) 5.0 min and tR
1
published data. H NMR l 1.27 (t, J=7.1 Hz, 3H),
1
(1R,2R) 5.6 min. H NMR l 1.25 (t, 3H, J=7.2 Hz),
1.3–2.1 (m, 10H), 2.59 (dt, 1H, J=2.7 and 9.8 Hz), 3.0
(m, 1H), 4.16 (m, 1H), 4.16 (q, J=7.1, 2H) ppm. 13C
NMR l 14.2 (CH3), 21.8 (CH2), 24.2 (CH2), 26.5
(CH2), 27.7 (CH2), 34.9 (CH2), 49.6 (CH), 60.6 (CH2),
70.2 (CH), 176.5 (CO) ppm.
1.7–2.1 (m, 9H), 2.8 (m, 1H), 4.35 (q, 2H, J=7.2 Hz),
5.3 (m, 1H) ppm. 13C NMR l 14.1 (CH3), 21.1 (CH3),
23.5 (CH2), 28.8 (CH2), 32.5 (CH2), 50.4 (CH), 60.6
(CH2), 78.3 (CH), 170.5 (CO), 174.2 (CO) ppm. ESIMS
m/z 223 [(M+Na)+, 100%], 201 [(M+H)+, 15%]. IR
(film) 1739 (CO) cm−1.
4.3.14. Ethyl (1S,2S)-2-hydroxycycloheptanecarboxyl-
ate, (1S,2S)-14. [h]D20 +17.3 (c 0.7, CHCl3) >99% e.e.
Lit.2b [h]D20 +15.0 (c 1.0, CHCl3) 93% e.e. The product
exhibited physical properties fully in agreement with the
published data. 1H NMR l 1.27 (t, 3H, J=7.2), 1.4–2.0
(m, 10H), 2.5 (dt, 1H, J=3.1 and 9.2 Hz), 2.52 (d, 1H,
J=3.6 Hz), 4.00 (ddd, 1H, J=3.7, 8.0 and 13.0 Hz),
4.20 (q, 2H, J= 7.2 Hz) ppm. 13C NMR l 14.2 (CH3),
22.4 (CH2), 26.5 (CH2), 27.0 (CH2), 27.8 (CH2), 35.5
(CH2), 53.5 (CH), 60.7 (CH2), 73.6 (CH), 175.1 (CO)
ppm.
4.3.9. Ethyl (1S,2R)-2-acetoxycyclohexanecarboxylate,
(1S,2R)-9. Colourless oil. Yield 75%. [h]2D0 −24.2 (c 1.1,
CHCl3) 99% e.e. GC conditions: RtbDEXse, 100°C 15
min, 100–170°C, 1°C/min, tR (1R,2S) 44.6 min and tR
1
(1S,2R) 45.4 min. H NMR l 1.21 (t, 3H, J=7 Hz),
1.25–2.2 (m, 11H), 2.50 (ddd, 1H, J=3, 8.8 and 8.8
Hz), 4.1 (m, 2H), 5.4 (m, 1H) ppm. 13C NMR l 14.1
(CH3), 20.3 (CH2), 21.1 (CH3), 23.1 (CH2), 24.1 (CH2),
29.5 (CH2), 45.4 (CH), 60.9 (CH2), 69.9 (CH), 170.2
(CO), 172.6 (CO) ppm. ESIMS m/z 237 [(M+Na)+,
18%], 215 [(M+H)+, 1%]. IR (film) 1740 (CO) cm−1.
Acknowledgements
4.3.10. Ethyl (1R,2R)-2-acetoxycyclohexanecarboxylate,
(1R,2R)-10. Colourless oil. Yield 95%. [h]2D0 −53.0 (c
1.3, CHCl3) >99% e.e. GC conditions: 100°C 15 min,
100–170°C, 1°C/min, tR (1S,2S) 46.7 min and tR
We express our appreciation to Novo Nordisk Co. for
the generous gift of the CALB. Financial support of
this work by the Spanish Ministerio de Ciencia y Tec-
nolog´ıa (Project PPQ-2001-2683) and by Principado de
Asturias (Project GE-EXP01-03) is gratefully acknowl-
edged. J.R.D. thanks the Spanish Ministerio de Educa-
cio´n, Cultura y Deporte for a predoctoral fellowship.
1
(1R,2R) 47.1 min. H NMR l 1.2 (t, 3H, J=7.0 Hz),
1.25–2.4 (m, 11H), 2.46 (ddd, 1H, J=3.8, 10.2 and 12.0
Hz), 4.12 (m, 2H), 5.0 (ddd, 1H, J=4.4, 10.3, 14.5 Hz)
ppm. 13C NMR l 14.2 (CH3), 21.1 (CH3), 23.8 (CH2),
24.4 (CH2), 28.4 (CH2), 30.8 (CH2), 48.8 (CH), 60.5
(CH2), 73.1 (CH), 170.0 (CO), 173.4 (CO) ppm. ESIMS
m/z 273 [(M+K)+, 20%], 237 [(M+Na)+, 20%], 215
[(M+H)+, 100%]. IR (film) 1740 (CO) cm−1.
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1
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