S. F. Mayer et al. / Tetrahedron: Asymmetry 12 (2001) 41–43
43
Acknowledgements
C7H14O2 (M+H)+: 129.091, found 129.088. (2R,3R)-2c:
1H NMR (CDCl3, 500 MHz) l=0.90 (t, J=7.2 Hz, 3H,
-CH
CH2), 1.92–1.94 (m, 2H, CH2), 2.17–2.19 (s, 1H, OH),
3.53 (dt, J=3.1 and 7.0 Hz, 1H, -CH-OH), 3.73 (dt,
J=4.8 and 9.2 Hz, 1H, -CH2AB-O-), 4.01 (dd, J=16 and
16 Hz, 1H, -CH2AB-O-), 4.18–4.20 (m, 1H, O-CH-n-Bu);
6 3), 1.33–1.37 (m, 4H, 2×CH2), 1.60–1.64 (m, 2H,
We wish to express our cordial thanks to H. Sterk
(University of Graz) for skillful assistance in NMR
spectroscopy and R. Saf (Graz University of Technol-
ogy) for MS measurements. This work was performed
within the Spezialforschungsbereich ‘Biokatalyse’ and
financial support by the Fonds zur Fo¨rderung der
wissenschaftlichen Forschung (Vienna, project no. F-
104) and the Austrian Ministry of Science is gratefully
acknowledged.
6
6
6
6
13C NMR (CDCl3, 90 MHz) l=14.1 (4%-C), 22.8 (3%-C),
28.2 (2%-C), 33.3 (1%-C), 35.2 (4-C), 66.2 (5-C), 76.3 (3-C),
86.5 (2-C); High resolution MS calcd for C8H16O2 (M+
H)+ 144.115, found 144.116.
10. Both compounds were diastereomerically pure.
11. Enantiomeric purities were analyzed on a Varian 3800
gas chromatograph equipped with FID. CP-Chirasil-
DEX CB column (25 m×0.32 mm, 0.25 mm film), 1b: 10
psi H2, iso 125°C, 9.24 min (2R,3S) and 10.13 min
(2S,3R); 1c: 10 psi H2, iso 80°C, 14.73 min (2S,3S) and
16.87 min (2R,3R); 5: 10 psi H2, iso 45°C, 14.54 min (2R)
and 15.25 min (2S). Astec Chiraldex B-TA capillary
column (30 m×0.25 mm), 2b: 10 psi H2, iso 120°C, 36.35
min (2R,3R) and 37.98 min (2S,3S); 2c: 10 psi H2, iso
95°C, 15.37 min (2S,3S) and 16.19 min (2R,3R).
12. (2R,3R)-1c: The optical rotation {[h]2D0=−3.1 (c=0.25,
CH2Cl2, e.e.=92%)} is in agreement with the reported
value {[h]2D0=−3.2 (c=1.3, CH2Cl2, e.e.=94%)}; see:
Vanhessche, K. P. M.; Wang, Z.-M.; Sharpless, B. K.
Tetrahedron Lett. 1994, 35, 3469–3472. (2R,3R)-2c:
[h]2D0=−24.4 (c=0.51, EtOH, e.e. >99%). The latter sam-
ple was obtained from an experiment stopped at low
conversion (ca. 30%).
13. The ratio of the reaction rates of enantiomers was calcu-
lated to be 8.6 and 1.9 for 1a and 2a, respectively. Details
will be published in a full paper.
14. Payne, G. B. J. Org. Chem. 1962, 27, 3819–3822.
15. Baldwin, J. E. J. Chem. Soc., Chem. Commun. 1976,
734–736.
16. Geigert, J.; Neidleman, S. L.; Liu, T.-N. E.; DeWitt, S.
K.; Panschar, B. M.; Dalietos, D. J.; Siegel, E. R. Appl.
Environ. Microbiol. 1983, 45, 1148–1152.
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8. SM refers to the culture collection of the Institute of
Biotechnology, Graz University of Technology. Racemic
epoxides rac-cis-1a (0.6 g, 4.05 mmol) and 2a (0.6 g, 3.69
mmol) were hydrolyzed using rehydrated lyophilized
microbial cells (1 g) in Tris buffer (20 mL, 0.05 M, pH
8.0) on a rotary shaker (120 rpm) at 30°C. When the
starting material was consumed (after 98 or 120 h, respec-
tively, as judged by TLC and GLC), the mixture was
extracted with EtOAc. The organic layers were dried
(Na2SO4) and evaporated. The residue was flash chro-
matographed (petrol ether/EtOAc, 10/1) to give (2R,3R)-
1c (92% e.e., 76% yield) and (2R,3R)-2c (86% e.e., 79%
yield).
17. Kroutil, W.; Mayer, S. F.; Faber, K. Fourth International
Electronic Conference on Synthetic Organic Chemistry
(ECSOC-4), T. Wirth, C. O. Kappe, E. Felder, U.
Diedrichsen, S.-K. Lin (Eds.), paper c C0019, MPDI,
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838–844. However, the stereochemical course of this reac-
tion was not investigated.
9. (2R,3R)-1c: 1H NMR (CDCl3, 200 MHz) l=0.91 (t,
J=6.9 Hz, 3H), 1.33–1.39 (m, 4H), 1.56–1.65 (m, 2H),
2.70–2.73 (m, 1H), 2.82 (dd, J=4.6 and 4.6 Hz, 1H), 2.98
(dd, J=4.9 and 4.9 Hz, 1H), 3.47 (dd, J=7.1 and 14.1
Hz, 1H); 13C NMR (CDCl3, 50 MHz) l=14.0, 22.7, 27.4,
34.2, 45.2, 55.4, 71.7; High resolution MS calcd for
.
.