JOURNAL OF CHEMICAL RESEARCH 2011 293
spectra were recorded on a Bruker ACF-300 spectrometer with TMS
as internal reference. The J values are given in hertz. Optical rotations
were determined on a Perkin-Elmer 343 polarimeter. The elemental
analyses were performed on a Perkin-Elmer 240C instrument.
General procedure for the simultaneously rapid deprotection of 3-
acyloxys group and reduction of D-ring ketones (nitrile) of steroids
using DIBAL-H/NiCl2
J = 8.7 Hz, 1H), 6.52 (d, J = 8.7 Hz, 1H), 6.47 (s, 1H), 3.64 (t, J = 8.4
Hz, 1H), 2.74 (m, 2H), 2.06 (m, 1H), 0.76 (s, 3H); 13C NMR (75 Hz,
CD3OD) δ 156.04, 138.95, 132.77, 127.37, 116.20, 113.87, 82.67,
51.44, 45.51, 44.52, 40.67, 38.18, 30.86(2C), 28.69, 27.75, 24.18,
11.86. Anal. Calcd for C18H24O2: C, 79.37; H, 8.88. Found: C, 79.15;
H, 8.70%.
Cholesterol (2g): Prepared from 3-acetylcholesterol (1g) according
to the above procedure. 2g (98 % yield) was obtained as needles: m.p.
148–150°C (EtOAc) (lit.21 148–150°C, EtOAc); [α]20D = –39.10° (c =
DIBALH (3.0 mL, 4.5 mmol, 1.5 M in toluene) and NiCl2 (19.5 mg,
0.15 mmol) was added to a solution of the steroid (1.5 mmol) in
dichloromethane (30 mL) under N2 at –78 °C. After an appropriate
reaction time (TLC showed that the starting material disappeared
completely), 1 N HCl (12 mL) was added. The reaction mixture was
warmed to room temperature and poured into water (50 mL) and
extracted with CH2Cl2 (3 × 15 mL). The combined organic phases
were washed with water (2 × 15 mL). Evaporation of the solvent gave
a white solid or an oil which was purified by chromatography (silica
gel, 10% EtOAc in CH2Cl2) to yield the anticipated steroids.
(3β,5α,17β)-Androstane-3,17-diol (2a): Prepared from (3β,5α)-3-
acetoxyandrostan- 17-one (1a) according to the above procedure. 2a
(99% yield) was obtained as needles: m.p. 168–170 °C (CHCl3), lit.
1
0.886, CHCl3); IR 3430, 1466, 1376, 1057 cm−1; H NMR (300 Hz,
CDCl3): δ 3.35 (d, J = 5.1 Hz, 1H), 3.52 (m, 1H), 1.01 (s, 3H), 0.91 (d,
J = 6.3 Hz, 3H), 0.86 (d, J = 6.3 Hz, 6H), 0.68 (s, 3H); 13C NMR (75
Hz, CDCl3): δ 140.74, 121.69, 71.76, 56.72, 56.11, 50.09, 42.27(2C),
39.74, 39.48, 37.22, 36.46, 36.15, 35.76, 31.86(2C), 31.63, 28.20,
27.92, 24.25, 23.80, 22.80, 22.54, 21.05, 19.37, 18.68, 11.82. Anal.
Calcd for C27H46O: C, 83.87; H, 11.99. Found: C, 83.65; H, 11.70%.
6β-Hydroxy cholestanol (2h): Prepared from 3β,6β-diacetoxy-5a-
cholestane (1h) according to the above procedure. 2h (96 % yield)
was obtained as needles: m.p. 168–150°C (EtOAc) (lit.22 168°C,
EtOAc); [α]20 = –32.16° (c = 0.572, CHCl3); IR 3438, 1400, 1380,
D
m.p. 161°C16; 163–165°C9; [α]20 = +6.20° (c = 0.550, CHCl3); IR
D
1006, 980, 786 cm−1; 1H NMR (300 Hz, CDCl3): δ 3.88 (m, 1H), 3.60
(m, 1H), 1.03 (s, 3H), 0.95 (d, J = 6.3 Hz, 3H), 0.91 (d, J = 6.3 Hz,
6H), 0.65 (s, 3H); 13C NMR (75 Hz, CDCl3): δ = 71.88, 71.20, 57.18,
56.78, 53.86, 47.22, 42.52(2C), 40.60, 39.78, 39.22, 37.30, 35.88,
35.76, 35.42, 31.36(2C), 30.40, 28.70, 27.86, 24.58, 23.53, 23.19,
21.06, 19.42, 16.50, 12.18. Anal. Calcd for C27H48O2: C, 80.14; H,
11.96; found C 80.02, H 11.78%.
3473, 3391, 3236, 1444, 1072, 1055, 1026 cm−1; H NMR δ 3.62
1
(m, 2H), 2.05 (m, 1H), 0.82 (s, 3H), 0.73 (s, 3H); 13C NMR δ 81.93,
71.25, 54.46, 51.00, 44.90, 42.97, 38.16, 37.02, 36.73(2C), 35.53,
31.60, 30.49, 28.55, 23.36, 20.81, 12.32, 11.11. Anal. Calcd for
C19H32O2: C, 78.03; H, 11.03. Found: C, 78.15; H, 11.20%.
(3β,17β)-Androst-5-ene-3,17-diol (2b): Prepared from (3β)-3-ace-
toxyandrost-5-en- 17-one (1b) according to the above procedure. 2b
(99% yield) was obtained as needles: m.p. 180–181°C (EtOAc) (lit.8
181°C, EtOAc); [α]20D = –51.31° (c = 0.267, MeOH); IR 3474, 3386,
We are grateful to the Natural Science Foundation of Jiangsu
Education Ministry of China (Grant 07KJB150135) and the
NSF of Jiangsu Province (Grant BK2008216) for financial
support.
1
3216, 1667, 1462, 1434, 1082, 1051, 1028 cm−1; H NMR (300 Hz,
CDCl3) δ 5.35 (d, J = 4.8 Hz, 1H), 3.65 (t, J = 8.7 Hz, 1H), 3.52 (m,
1H), 2.27 (m, 2H), 2.04 (m, 2H), 1.02 (s, 3H), 0.76 (s, 3H); 13C NMR
(75 Hz, CD3OD) δ 142.48, 122.40, 82.62, 72.56, 52.85, 52.05, 44.00,
43.19, 38.74, 38.04, 37.92, 33.47, 32.79, 32.44, 30.78, 24.52, 21.97,
20.07, 11.67. Anal. Calcd for C19H30O2: C, 78.57; H, 10.41. Found:
C, 78.65; H, 10.20%.
Received 26 March 2011; accepted 18 April 2011
Paper 1100631 doi: 10.3184/174751911X13050949941793
Published online: 1 June 2011
3-((2R,4aS,4bS,8S,8aS,10aS)-Tetradecahydro-2-hydroxy-4a-
methyl-7-methylenephenanthren-8-yl)propanal (2c):17 Prepared from
(1S,4aS,4bS,7R,8aS,10aS)-1-(2-cyanoethyl)-tetradecahydro-4b-
methyl-2-methylenephenanthren-7-yl benzoate (1c) according to the
References
1
2
3
4
5
A.S. Lamm, A.R.M. Chen, W.F. Reynolds and P.B. Reese, Steroids, 2007,
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above procedure. 2c (90 % yield) was obtained as an oil: [α]20 = –
D
24.58° (c = 0.8625, CHCl3); IR 3401, 3080, 2718, 1722, 1643 cm−1;
1H NMR δ 9.71 (t, J = 1.2 Hz, 1H), 4.67 (s, 1H), 4.41 (s, 1H), 3.97 (m,
1H), 0.63 (s, 3H); 13C NMR δ 202.74, 150.60, 104.69, 66.06, 53.17,
47.63, 41.92, 38.25, 36.82, 36.18, 35.47, 31.95, 31.51, 28.72, 28.25,
27.14, 19.26, 10.90. Anal. Calcd for C19H30O2: C, 78.57; H, 10.41.
Found: C, 78.70; H, 10.24%.
M.H. Whitnall, T.B. Elliott, R.A. Harding, C.E. Inal, M.R. Landauer and
C.L. Wilhelmsen, Int. J. Immunopharmacol., 2000, 22, 1.
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3-((2S,4aS,4bS,8S,8aS,10aS)-Tetradecahydro-2-hydroxy-4a-
methyl-7-methylenephenanthren-8-yl)propanal (2d): Prepared from
(1S,4aS,4bS,7S,8aS,10aS)-1-(2-cyanoethyl)-tetradecahydro-4b-
methyl-2-methylenephenanthren-7-yl acetate (1d) according to the
6
7
T.H. Lippert, H. Seeger and A.O. Mueck, Steroids, 2000, 65, 357.
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above procedure. 2d (92 % yield) was obtained as an oil: [α]20
=
D
–21.10° (c = 4.322, CHCl3); IR 3391, 3080, 2720, 1722, 1643 cm−1;
1H NMR δ 9.77 (t, J = 1.2 Hz, 1H), 4.73 (s, 1H), 4.47 (s, 1H), 3.59
(m, 1H), 0.73 (s, 3H); 13C NMR δ 202.74, 150.45, 104.81, 70.88,
53.22, 47.60, 44.03, 42.00, 41.33, 37.72, 36.84, 36.78, 35.65, 31.60,
31.16, 28.38, 27.58, 19.31, 12.04. Anal. Calcd for C19H30O2: C, 78.57;
H, 10.41. Found: C, 78.75; H, 10.20%.
8
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Steroids, 2005, 70, 907.
(3β, 17β, 20β)-Pregn-5-en-3,20-diol (2e): Prepared from (3β, 17β)-
3-acetoxypregn-5-en-20-one (1e) according to the above procedure.
2e (99 % yield) was obtained as needles: m.p. 211–212°C (MetOH)
(lit.18–19 211–211.5°C, EtOH); [α]20D = –77.42° (c = 0.186, MeOH); IR
1
3422, 3386, 1639, 1464, 1436, 1376, 1053 cm−1; H NMR (300 Hz,
CD3OD) δ 5.34 (d, J = 5.1 Hz, 1H), 3.63 (m, 1H), 3.38 (m, 1H), 1.10
(d, J = 6.3 Hz, 3H), 1.03 (s, 3H), 0.78 (s, 3H); 13C NMR (75 Hz,
CD3OD) δ 142.44, 122.54, 72.59, 70.99, 59.49, 57.86, 52.02, 43.64,
43.19, 40.95, 38.72, 37.87, 33.30, 33.26, 32.45, 26.96, 25.76, 23.92,
22.19, 20.04, 12.74. Anal. Calcd for C21H34O2: C, 79.19; H, 10.76.
Found: C, 79.05; H, 10.50%.
17β-Estradiol (2f): Prepared from 3-acetoxy-1,3,5(10)-estratrien-
17-one (1f) according to the above procedure. 2f (99 % yield) was
obtained as needles: m.p. 174–176°C (MeOH) (lit.20 178–179.5°C);
[α]20 = +80.10° (c = 0.586, dioxane); IR 3531, 3403, 1614, 1585,
D
1497, 1449, 1251, 1054 cm−1; 1H NMR (300 Hz, CD3OD) δ 7.06 (d,