˚
l = 0.71073 A). The strategy for the data collection was evaluated
(4-C), 44.3 (13-C), 50.1 (9-C), 52.3 (14-C), 72.2 (3-C), 74.0 (7-C),
82.3 (17-C), 127.4 (6-C), 144.1 (5-C).
by using the CrysAlis CCD software. Data reduction and analysis
were carried out with the CrysAlis RED program. The structure
was solved by direct methods using SHELXS9742 program and
refined using all F2 data, as implemented by the SHELXL97
program.
3b,17b-Dihydroxyandrost-5-en-7-one (9): (17.1 mg, 8.2%); mp
202–204 ◦C (from methanol) (lit.,45 201 ◦C); Found: C, 74.88; H,
9.25. C19H28O3 requires C, 74.96; H, 9.27%. IR nmax/cm-1 3304,
1651, 1615. 1H-NMR (300 MHz, CDCl3) dH: 0.75 (3H, s, 18-Me);
1.20 (3H, s, 19-Me); 3.62–3.69 (1H, m, 3a-H); 3.64, t, J = 10.8 Hz,
17a-H); 5.68 (1H, d, J = 1.5 Hz, 6-H). 13C-NMR (75 MHz, CDCl3)
dC: 11.0 (18-C), 17.4 (19-C), 20.9 (11-C), 25.8 (15-C), 30.7 (16-C),
31.2 (2-C), 35.6 (12-C), 36.4 (1-C), 38.4 (10-C), 41.8 (4-C), 43.3
(13-C), 44.9 (14-C), 45.2 (8-C), 50.0 (9-C), 70.4 (3-C), 81.0 (17-C),
125.9 (6-C), 165.5 (5-C), 201.9 (7-C).
Products isolated in the course of transformations
7a-Hydroxy-DHEA (4): (90.3 mg, 53.5%); mp 181–182 ◦C (from
acetone) (lit.,21 179.4–181.7 ◦C); Found: C, 74.88; H, 9.24.
C19H28O3 requires C, 74.96; H, 9.27%. IR nmax/cm-1 3360, 2932,
1736, 1620. 1H-NMR (300 MHz, CDCl3) dH: 0.88 (3H, s, 18-Me);
1.01 (3H, s, 19-Me); 3.56–3.61 (1H, m, 3a-H); 3.97 (1H, t, J =
3.6 Hz, 7b-H); 5.64 (1H, d, J = 5.0 Hz, 6-H). 13C-NMR (75 MHz,
CDCl3) dC: 13.0 (18-C), 18.0 (19-C), 19.8 (11-C), 21.6 (15-C), 30.8
(2-C), 31.0 (12-C), 35.5 (16-C), 36.6 (10-C), 36.9 (1-C), 37.2 (8-C),
41.6 (4-C), 42.3 (13-C), 44.6 (9-C), 46.8 (14-C), 64.0 (7-C), 70.9
(3-C), 123.3 (6-C), 146.3 (5-C), 220.0 (17-C).
7a-Hydroxy-EpiA (10): (154 mg, 73%); mp 194 ◦C (from
acetone) (lit.,46 194–195 ◦C); Found: C, 74.41; H, 9.88. C19H30O3
1
requires C, 74.47; H, 9.87%. IR nmax/cm-1 3600, 3418, 1739. H-
NMR (300 MHz, CDCl3) dH: 0.83 (3H, s, 19-Me); 0.86 (3H, s,
18-Me); 3.56–3.66 (1H, m, 3a-H); 3.93–3.96 (1H, m, 7b-H). 13C-
NMR (75 MHz, CDCl3) dC: 11.2 (19-C), 13.5 (19-C), 20.3 (11-C),
21.3 (15-C), 31.3 (12-C), 31.4 (2-C), 35.7 (6-C), 36.0 (10-C), 36.6
(1-C), 36.6 (16-C), 37.0 (5-C), 37.5 (4-C), 39.1 (8-C), 45.8 (14-C),
46.1 (10-C), 47.5 (13-C), 66.7 (7-C), 70.9 (3-C), 221.1 (17-C).
11a-hydroxy-EpiA (11): (13 mg, 6.9%); mp 103–104 ◦C (from
acetone) (lit.,47 103–106 ◦C); Found: C, 74.40; H, 9.88. C19H30O3
7b-Hydroxy-DHEA (5): (40.5 mg, 24%); mp 215–217 ◦C (from
acetone) (lit.,21 216.2–217.6 ◦C); Found: C, 74.89; H, 9.25.
C19H28O3 requires C, 74.96; H, 9.27%. IR nmax/cm-1 3229, 2933,
1733. 1H-NMR (300 MHz, CDCl3) dH: 0.89 (3H, s, 18-Me); 1.07
(3H, s, 19-Me); 3.53-3.58 (1H, m, 3a-H); 3.95 (1H, dt, J = 2.1 Hz,
J = 7.8 Hz, 7a-H); 5.31 (1H, t, J = 1.8 Hz, 6-H). 13C-NMR
(75 MHz, CDCl3) dC: 13.5 (18-C), 19.1 (19-C), 20.3 (11-C), 24.1
(15-C), 31.1 (2-C), 31.4 (12-C), 35.9 (16-C), 36.6 (10-C), 36.8 (1-
C), 40.4 (8-C), 41.5 (4-C), 47.7 (13-C), 48.1 (9-C), 51.1 (14-C), 72.8
(7-C), 71.2 (3-C), 125.4 (6-C), 143.6 (5-C), 221.2 (17-C).
1
requires C, 74.47; H, 9.87%. IR nmax/cm-1 3470, 1741. H-NMR
(300 MHz, CDCl3) dH: 0.86 (3H, s, 18-Me); 0.94 (3H, s, 19-Me);
3.52-3.63 (1H, m, 3a-H); 3.96 (1H, dt, J = 5.2, J = 10.4 Hz, 11b-H).
13C-NMR (75 MHz, CDCl3) dC: 12.7 (19-C), 14.5 (18-C), 21.8 (15-
C), 28.9 (6-C), 30.7 (7-C), 31.7 (2-C), 34.2 (8-C), 35.8 (16-C), 37.3
(10-C), 38.5 (1-C), 38.5 (4-C), 42.9 (12-C), 45.0 (5-C), 48.0 (13-C),
50.3 (14-C), 60.5 (9-C), 68.6 (11-C), 70.7 (3-C), 219.5 (17-C).
9a-hydroxy-EpiA (12): (19 mg, 9%); mp 191–192 ◦C (from
acetone) (lit.,31 192–193 ◦C); Found: C, 74.40; H, 9.86. C19H30O3
7-Oxo-DHEA (6): (10 mg, 6%); mp 239 ◦C (from methanol)
◦
(lit.,43 236–239 C); Found: C, 75.42; H, 8.65. C19H26O3 requires
C, 75.46; H, 8.66%. IR nmax/cm-1 3482, 1728, 1654, 1610. 1H-NMR
(300 MHz, CDCl3) dH: 0.90 (3H, s, 18-Me); 1.23 (3H, s, 19-Me);
3.65-3.73 (1H, m, 3a-H); 5.75 (1H, d, J = 1.5 Hz, 6-H). 13C-NMR
(75 MHz, CDCl3) dC: 13.7 (18-C), 17.4 (19-C), 20.6 (11-C), 24.2
(15-C), 30.7 (12-C), 31.1 (2-C), 35.6 (16-C), 36.3 (10-C), 38.4 (1-
C), 41.8 (4-C), 44.3 (14-C), 45.7 (8-C), 47.8 (13-C), 50.0 (9-C), 70.3
(3-C), 126.0 (6-C), 166.0 (5-C), 201.0 (7-C), 220.4 (17-C).
requires C, 74.47; H, 9.87%. IR nmax/cm-1 3344, 1740. H-NMR
1
(300 MHz, CDCl3) dH: 0.85 (3H, s, 18-Me); 0.95 (3H, s, 19-Me);
3.53-3.64 (1H, m, 3a-H). 13C-NMR (75 MHz, CDCl3) dC: 12.7
(18-C), 14.2 (19-C), 24.5 (7-C), 25.6 (15-C), 26.9 (11-C), 27.2 (6-
C), 28.1 (12-C), 29.8 (1-C), 31.1 (2-C), 35.8 (16-C), 36.3 (5-C), 37.2
(8-C), 38.0 (4-C), 40.3 (10-C), 44.2 (14-C), 47.6 (13-C), 70.7 (3-C),
75.7 (9-C), 220.8 (17-C).
3b,7a,17b-Trihydroxyandrost-5-ene (7): (101.2 mg, 47.9%); mp
205–208 ◦C (from methanol) (lit.,44 205 ◦C); Found: C, 74.38; H,
9.85. C19H30O3 requires C, 74.47; H, 9.87%. IR nmax/cm-1 broad
absorption around 3300. 1H-NMR (300 MHz, CD3OD) dH: 0.75
(3H, s, 18-Me); 1.02 (3H, s, 19-Me); 3.44–3.55 (1H, m, 3a-H); 3.61
(1H, t, J = 8.5 Hz, 17a-H); 3.76 (1H, t, J = 3.6 Hz, 7b-H); 5.54 (1H,
d, J = 5.0 Hz, 6-H). 13C-NMR (75 MHz, CD3OD) dC: 11.4 (18-C),
18.7 (19-C), 21.5 (11-C), 24.2 (15-C), 30.7 (16-C), 32.2 (2-C), 37.5
(12-C), 38.2 (C-1), 38.5 (10-C), 39.1 (8-C), 42.9 (4-C), 43.6 (13-C),
43.7 (9-C), 45.4 (14-C), 65.5 (7-C), 72.0 (3-C), 82.5 (17-C), 125.0
(6-C), 146.7 (5-C).
Acknowledgements
This research was supported financially by the European Union
within the European Regional Development Found (grant No.
POIG.01.03.01-00-158/09-02).
References
1 D. L. Auci, C. L. Reading and J. M. Frincke, Autoimmun. Rev., 2009,
8, 369–372.
2 R. Lathe, Steroids, 2002, 67, 967–977.
3b◦,7b,17b-Trihydroxyandrost-5-ene (8): (46 mg, 21.8%); mp 231–
233 C (from methanol) (lit.,45 236 ◦C); Found: C, 74.39; H,
9.86. C19H30O3 requires C, 74.47; H, 9.87%. IR nmax/cm-1 broad
absorption around 3510. 1H-NMR (300 MHz, CD3OD) dH: 0.76
(3H, s, 18-Me); 1.09 (3H, s, 19-Me); 3.37-3.48 (1H, m, 3a-H); 3.56
(1H, t, J = 8.5 Hz, 17a-H); 3.72 (1H, dt, J = 2.1 Hz, J = 7.8 Hz,
7a-H); 5.25 (1H, t, J = 1.8 Hz, 6-H). 13C-NMR (75 MHz, CD3OD)
dC: 11.6 (18-C), 19.6 (19-C), 21.9 (11-C), 26.6 (15-C), 30.9 (16-C),
32.3 (2-C), 37.7 (10-C), 37.8 (12-C), 38.3 (1-C), 41.3 (8-C), 42.6
3 S. Chalbot and R. Morfin, Steroids, 2005, 70, 319–326.
4 S-B. Kim, S. Chalbot, D. Pompon, D-H. Jo and R. Morfin, J. Steroid
Biochem. Mol. Biol., 2004, 92, 383–389.
5 K. A. Rose, G. Stapleton, K. Dott, M. P. Kieny, R. Best, M. Schwarz,
D. W. Russell, I. Bjo¨rkhem, J. Seckl and R. Lathe, Proc. Natl. Acad.
Sci. U. S. A., 1997, 94, 4925–4930.
6 S. Chalbot, C. Trap, J-P. Monin and R. Morfin, Steroids, 2002, 67,
1121–1127.
7 H. Lardy, A. Marwah and P. Marwah, Lipids, 2002, 37, 1187–1190.
8 S. Chalbot and R. Morfin, Drug Metab. Dispos., 2005, 33, 563–569.
9 A. Li and J. C. Bigelow, Steroids, 2010, 75, 404–410.
This journal is
The Royal Society of Chemistry 2011
Org. Biomol. Chem., 2011, 9, 5414–5422 | 5421
©