1
280
Yildirim:
08–209 °C, [α]D +67, c 0.1, CHCl3 (lit.30 gives m.p. 213–215 °C, [α]D +63, c 1.3, CHCl ). For
2
0
20
2
3
C19H28O3 (304.41) calculated: 74.96% C, 9.27% H; found: 74.75% C, 9.03% H. IR: 3237
1
(
(
O–H), 1736 (C=O), 1665 (C=C). H NMR (300 MHz, CDCl ): 0.90 s, 3 H (H-18); 1.08 s, 3 H
3
H-19); 3.50 tt, 1 H, J(3,2) = 5.0, J(3,4) = 10.0 (H-3); 3.95 dt, 1 H, J(7α,8) = 8.0, J(7α,6) =
J(7α,4β) = 3.0 (H-7); 5.32 bs (H-6). C NMR (75 MHz, CDCl ): 221.33, 143.64, 125.44,
1
3
3
7
2
2.79, 71.19, 51.12, 48.16, 47.75, 41.57, 40.38, 36.82, 36.61, 35.96, 31.40, 31.16, 24.16,
0.34, 19.14, 13.55.
Elution with pure ethyl acetate in hexane afforded 3β,7α-dihydroxyandrost-5-en-17-one
(
7; 269 mg, 51%), which was crystallized from ethyl acetate–petroleum ether as needles,
20
30
20
m.p. 174–175 °C, [α]D –73, c 0.1, CHCl3 (lit. gives m.p. 178–180 °C, [α]D –80, c 0.14,
CH OH). For C19H28O3 (304.41) calculated: 74.96% C, 9.27% H; found: 74.81% C, 9.10% H.
3
1
IR: 3347 (O–H), 3163 (O-H), 1734 (C=O), 1622 (C=C). H NMR (300 MHz, CDCl ): 0.89 s,
3
3
5
6
1
H (H-18); 1.03 s, 3 H (H-19); 3.56 m, 1 H, W = 24 (H-3); 3.96 bs, 1 H, Wh = 12 (H-7);
h
.63 d, 1 H, J(6,7β) = 5.0 (H-6). 1 C NMR (75 MHz, CDCl ): 221.89, 145.97, 123.30, 70.75,
3
3
3.89, 47.01, 44.69, 42.24, 41.64, 37.25, 36.98, 36.73, 35.65, 30.84 (2 × C), 21.67, 19.84,
8.07, 13.08.
Biotransformation of Pregnenolone (3) by A. wentii
Under similar conditions, the incubation of pregnenolone (3; 500 mg, 1.58 mmol) with
A. wentii afforded a brown gum (753 mg), which was then chromatographed on a silica gel.
Elution with 30% ethyl acetate in hexane afforded the unreacted starting material (60 mg,
1
13
1
2%), which was identified by comparison of its H and C NMR spectra with those of an
authentic material.
Elution with 50% ethyl acetate in hexane afforded 11α-hydroxypregn-4-ene-3,20-dione
(
[
(
(
8; 407 mg, 78%), which was crystallized from ethyl acetate as needles, m.p. 163–164 °C,
20
31
20
α] +165, c 0.1, CHCl3 (lit. gives m.p. 165–167 °C, [α]D +169, CHCl ). For C21H30O3
D
3
330.45) calculated: 76.32% C, 9.15% H; found: 76.21% C, 9.08% H. IR: 3380 (O–H), 1654
C=O), 1610 (C=C). 1H NMR (300 MHz, CDCl ): 0.65 s, 3 H (H-18); 1.28 s, 3 H (H-19);
3
2
1
5
1
.10 s, 3 H (H-21); 3.98 dt, 1 H, J(11β,12β) = 5.0, J(11β,9) = J(11β,12α) = 10.0 (H-11); 5.69 s,
1
3
H (H-4). C NMR (75 MHz, CDCl ): 209.02, 200.49, 171.40, 124.34, 68.63, 63.02, 58.77,
3
5.21, 50.18, 44.04, 39.86, 37.32, 34.82, 34.06, 33.51, 31.43, 31.27, 24.12, 22.83, 18.18,
4.38.
The author would like to thank F. Sonmez and H. Genc for running the 1H and 13C NMR spectra.
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3
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