2780
J.F.S. Carvalho et al. / Tetrahedron 65 (2009) 2773–2781
4.3.22. 4
b
,5
b
-Epoxycholestan-3
b
-yl acetate (11b)
4.3.30. 5
1H NMR (300 MHz, CDCl3)
19-CH3), 2.03 (3H, s, 3 -CH3COO), 2.25 (3H, s, 21-CH3), 3.11 (1H, d,
J¼2.4 Hz, 6 -H), 4.77 (1H, tdd, J¼11.4, 9.6, 4.7, 4.7 Hz, 3 -H), 6.68
(dd, J¼3.2, 1.9 Hz, 16-H).
b
,6
b
-Epoxy-20-oxo-pregn-16-en-3
b-yl acetate (16b)
Mp 89–90 ꢀC (EtOH); lit.37 89–90 ꢀC; 1H NMR (300 MHz, CDCl3)
d
ppm 0.87 (3H, s,18-CH3),1.04 (3H, s,
d
ppm 0.68 (3H, s,18-CH3), 0.86 and 0.87 (each 3H, 2d, J¼6.6 Hz, 26-
b
CH3 and 27-CH3), 0.90 (3H, d, J¼6.6 Hz, 21-CH3), 1.04 (3H, s, 19-
a
a
CH3), 2.10 (1H, s, 3
b
-CH3COO), 3.16 (1H, d, J¼3.6 Hz, 4
a-H), 5.13 (1H,
m, 3
a
-H); 13C NMR (75 MHz, CDCl3)
d
ppm 11.9, 18.4, 18.6, 21.2, 21.4,
22.5 (2C), 22.8, 23.8, 24.2, 28.0, 28.1, 29.6, 30.3, 31.2, 35.2, 35.7, 35.8
(C-10), 36.1, 39.5, 39.7, 42.5 (C-13), 49.0, 56.0, 56.2, 61.3, 66.8 (C-5),
69.0, 171.0 (CH3COO).
4.3.31. (22E)-5 ,6 -Epoxystigmast-22-en-3
a
a
b
-ol (17a)
Mp 155–155.5 ꢀC (EtOH); lit.43 149–151 ꢀC; 1H NMR (300 MHz,
CDCl3)
d
ppm 0.63 (3H, s, 18-CH3), 0.79 (3H, d, J¼6.6 Hz, 26-CH3), 0.80
(3H, t, J¼6.6, 6.6 Hz, 242-CH3), 0.84 (3H, d, J¼6.6 Hz, 27-CH3), 0.99 (3H,
4.3.23. 4
a
,5
a
-Epoxycholestan-3
a-ol (12a)
d, J¼6.6 Hz, 21-CH3), 1.06 (3H, s,19-CH3), 2.90 (1H, d, J¼4.4 Hz, 6
b-H),
Mp 92–93 ꢀC (EtOH); lit.38 92–94 ꢀC; 1H NMR (300 MHz, CDCl3)
3.91 (1H, tt, J¼11.2,11.2, 4.8, 4.8 Hz, 3
a-H), 5.00 and 5.13 (each 1H, 2dd,
d
ppm 0.68 (3H, s,18-CH3), 0.86 and 0.87 (each 3H, 2d, J¼6.6 Hz, 26-
J¼15.2, 8.4 Hz, 22-H and 23-H); 13C NMR (75 MHz, CDCl3)
d ppm 12.0,
CH3 and 27-CH3), 0.90 (3H, d, J¼6.6 Hz, 21-CH3),1.02 (3H, s,19-CH3),
12.2,15.9,18.9, 20.6,21.1, 21.1, 24.1, 25.4, 28.8,29.9, 31.0, 31.8,32.4, 34.8,
39.3, 39.8, 40.4, 42.2 (C-13), 42.6, 51.2, 51.3, 55.6, 56.9, 59.3, 65.7 (C-5),
68.7, 129.3 and 138.2 (C-22 and C-23).
3.19 (1H, dd, J¼4.5, 0.6 Hz, 4
b
-H), 4.03 (1H, ddd, J¼5.1, 4.5, 0.6 Hz, 3
b-
H); 13C NMR (75 MHz, CDCl3)
d
ppm 12.0, 17.3, 18.6, 20.7, 22.5, 22.8,
23.8, 24.1, 27.0, 27.7, 28.0, 28.2, 28.5, 29.8, 35.4, 35.4 (C-10), 35.8, 36.1,
39.5, 39.7, 42.6 (C-13), 50.4, 55.7, 56.1, 63.1, 63.1, 69.6 (C-5).
4.3.32. (22E)-5
b
,6
b
-Epoxystigmast-22-en-3
b
-ol (17b)
1H NMR (300 MHz, CDCl3)
d
ppm 0.66 (3H, s, 18-CH3), 0.79 (3H,
4.3.24. 4
1H NMR (300 MHz, CDCl3)
0.87 (each 3H, 2d, J¼6.6 Hz, 26-CH3 and 27-CH3), 0.94 (3H, d,
J¼6.6 Hz, 21-CH3), 1.01 (3H, s, 19-CH3), 2.85 (1H, d, J¼0.9 Hz, 4 -H),
3.98 (1H, m, 3 -H).
b,5
b-Epoxycholestan-3
a-ol (12b)
d, J¼6.6 Hz, 26-CH3), 0.80 (3H, t, J¼6.6, 6.6 Hz, 242-CH3), 0.84 (3H, d,
d
ppm 0.68 (3H, s, 18-CH3), 0.87 and
J¼6.6 Hz, 27-CH3), 0.99 (3H, d, J¼6.6 Hz, 21-CH3), 1.00 (3H, s, 19-
CH3), 3.06 (1H, d, J¼2.5 Hz, 6
a-H), 3.70 (1H, m, 3a-H), 5.00 and 5.13
a
(each 1H, 2dd, J¼15.2, 8.5 Hz, 22-H and 23-H).
b
4.3.33. 4 ,5 -Epoxycholestan-3-one (18a)
a
a
4.3.25. 5
Mp 138.5–139.5 ꢀC (EtOH); lit.39 139–140 ꢀC; 1H NMR (600 MHz,
CDCl3) ppm 0.63 (3H, s, 18-CH3), 0.86 and 0.87 (each 3H, 2d,
J¼6.6 Hz, 26-CH3 and 27-CH3), 0.89 (3H, s, 19-CH3), 0.90 (3H, d,
J¼6.6 Hz, 21-CH3), 3.26 (1H, s, 6 -H), 3.96 (1H, m, 3
-H); 13C NMR
(75 MHz, CDCl3) ppm 12.1, 15.4, 18.7, 20.9, 22.5, 22.8, 23.9, 24.2,
a
,6
a
-Epoxy-7-norcholestan-3
b
-ol (13a)
Mp 121–123 ꢀC (EtOH); lit.44 120–121 ꢀC; 1H NMR (300 MHz,
CDCl3) ppm 0.70 (3H, s, 18-CH3), 0.86 and 0.87 (each 3H, 2d,
J¼6.5 Hz, 26-CH3 and 27-CH3), 0.91 (3H, d, J¼6.5 Hz, 21-CH3), 1.05
(3H, s, 19-CH3), 3.04 (1H, s, 4 ppm
-H); 13C NMR (75 MHz, CDCl3)
12.0, 16.5, 18.6, 21.4, 22.5, 22.8, 23.8, 24.2, 28.0, 28.1, 28.9, 28.9, 29.1,
33.1, 35.4, 35.8, 36.1, 36.7 (C-10), 39.5, 39.7, 42.5 (C-13), 50.7, 55.6,
56.2, 62.9 (C-4), 70.2 (C-5), 207.1 (C-3).
d
d
b
d
b
a
d
28.0, 28.5, 30.9, 31.2, 34.6, 35.7, 36.2, 38.8 (C-10), 39.4, 39.8, 42.5,
44.4 (C-13), 48.2, 50.6, 55.5, 60.4, 69.1 (C-5), 69.8.
4.3.34. 4
1H NMR (300 MHz, CDCl3)
0.87 (each 3H, 2d, J¼6.5 Hz, 26-CH3 and 27-CH3), 0.90 (3H, d,
J¼6.5 Hz, 21-CH3), 1.15 (3H, s, 19-CH3), 2.98 (1H, s, 4 -H).
b
,5
b
-Epoxycholestan-3-one (18b)
4.3.26. 5
Mp 113–113.5 ꢀC (EtOH); lit.40 111–112 ꢀC; 1H NMR (600 MHz,
CDCl3) ppm 0.63 (3H, s, 18-CH3), 0.86 and 0.87 (each 3H, 2d,
J¼6.6 Hz, 26-CH3 and 27-CH3), 0.90 (3H, s, 19-CH3), 0.91 (3H, d,
J¼6.6 Hz, CH3-21), 2.03 (3H, s, 3 -CH3COO), 3.26 (1H, s, 6 -H), 4.98
(1H, tt, J¼11.2, 11.2, 4.8, 4.8 Hz, 3
-H); 13C NMR (75 MHz, CDCl3)
ppm 12.0, 15.3, 18.6, 20.8, 21.3, 22.5, 22.7, 23.8, 24.2, 26.9, 27.9,
a
,6
a
-Epoxy-7-norcholestan-3
b
-yl acetate (14a)
d
ppm 0.68 (3H, s, 18-CH3), 0.86 and
d
a
b
b
4.3.35. 4 ,5 -Epoxypregnane-3,20-dione (19a)
a a
a
Mp 178–179 ꢀC (EtOH); lit.28 177–178 ꢀC; 1H NMR (300 MHz,
CDCl3) ppm 0.65 (3H, s, 18-CH3), 1.05 (3H, s, 19-CH3), 2.12 (3H, s,
21-CH3), 3.04 (1H, s, 4 ppm 13.3,
-H); 13C NMR (75 MHz, CDCl3)
d
d
28.5, 30.9, 31.1, 35.6, 36.1, 38.7 (C-10), 39.4, 39.7, 42.4, 44.4 (C-13),
48.0, 50.5, 55.5, 60.3, 68.3 (C-5), 72.1, 170.1 (CH3COO).
b
d
16.5, 21.4, 22.8, 24.4, 28.8, 29.1, 29.6, 31.5, 33.0, 35.3, 36.7 (C-10),
38.7, 44.0 (C-13), 50.5, 55.8, 62.8, 63.6, 70.0 (C-5), 206.9 (C]O),
209.5 (C]O).
4.3.27. 5
Mp 172–174 ꢀC (EtOH); lit.41 140–143 ꢀC; 1H NMR (300 MHz,
CDCl3) ppm 0.85 (3H, s, 18-CH3), 1.10 (19-CH3), 2.25 (3H, s, 21-
a,6a-Epoxy-3b-hydroxy-pregn-16-en-20-one (15a)
d
4.3.36. 4
1H NMR (300 MHz, CDCl3)
19-CH3), 2.12 (3H, s, 21-CH3), 2.99 (1H, s, 4a
b
,5b
-Epoxypregnane-3,20-dione (19b)
ppm 0.64 (3H, s, 18-CH3), 1.15 (3H, s,
-H).
CH3), 2.93 (1H, d, J¼4.5 Hz, 6
b
-H), 3.91 (1H, tt, J¼11.3, 11.3, 4.8,
d
4.8 Hz, 3
CDCl3)
a
-H), 6.68 (1H, dd, J¼3.4, 1.9 Hz, 16-H); 13C NMR (75 MHz,
d
ppm 15.6, 15.9, 20.3, 27.1, 28.2, 28.4, 31.0, 32.0, 32.2, 34.2,
35.0 (C-10), 39.8, 42.7, 46.0 (C-13), 56.3, 58.9, 65.9, 68.6, 144.2 (C-
16), 155.1 (C-17), 196.8 (C-20).
4.3.37. 4
Mp 169–170 ꢀC (EtOH); lit.28 169–171 ꢀC; 1H NMR (300 MHz,
CDCl3) ppm 0.78 (3H, s,18-CH3),1.07(3H, s,19-CH3), 3.04 (1H, s, 4
-H); 13C NMR (75 MHz, CDCl3)
ppm
11.0,16.5, 21.0, 23.3, 28.5, 29.1, 29.6, 30.4, 33.1, 35.4, 36.4, 36.7 (C-10),
42.9 (C-13), 50.2, 50.8, 62.8, 70.1 (C-5), 81.6, 207.0 (C]O).
a,5a-Epoxy-17b-hydroxy-androstan-3-one (20a)
d
b-
4.3.28. 5
1H NMR (300 MHz, CDCl3)
19-CH3), 2.25 (3H, s, 21-CH3), 3.10 (1H, d, J¼2.5 Hz, 6
m, 3 -H), 6.69 (1H, m, 16-H).
b,6
b
-Epoxy-3
b
-hydroxy-pregn-16-en-20-one (15b)
ppm 0.88 (3H, s,18-CH3),1.03 (3H, s,
-H), 3.70 (1H,
H), 3.67 (1H, t, J¼8.5, 8.5 Hz,17
a
d
d
a
a
4.3.38. 4
1H NMR (300 MHz, CDCl3)
(3H, s, 19-CH3), 2.98 (1H, s, 4
17 -H).
b,5b-Epoxy-17b-hydroxy-androstan-3-one (20b)
4.3.29. 5
Mp 189–190 ꢀC (EtOH); lit.42 170–172 ꢀC; 1H NMR (300 MHz,
CDCl3) ppm 0.84 (3H, s,18-CH3),1.11 (3H, s,19-CH3), 2.01 (3H, s, 3
a
,6
a
-Epoxy-20-oxo-pregn-16-en-3
b
-yl acetate (16a)
d
ppm 0.77 (3H, s, 18-CH3), 1.16
b
-H), 3.67 (1H, t, J¼8.5, 8.5 Hz,
d
b
-
a
CH3COO), 2.24 (3H, s, 21-CH3), 2.92 (1H, d, J¼4.5 Hz, 6
b-H), 4.94 (tt,
J¼11.4, 11.4, 5.0, 5.0 Hz, 3
a
-H), 6.67 (1H, dd, J¼3.2, 1.9 Hz, 16-H); 13
C
Acknowledgements
NMR (75 MHz, CDCl3)
d
ppm 15.6,15.8, 20.3, 21.3, 27.1, 27.1, 28.1, 28.3,
ˆ
31.9, 31.9, 34.1, 35.1 (C-10), 36.0, 42.6, 46.0 (C-13), 56.2, 58.7, 65.3 (C-
5), 71.2, 144.1 (C-16), 155.1 (C-17), 170.2 (CH3COO), 196.7 (C-20).
We thank Fundaça˜o para a Ciencia e Tecnologia (FCT), Portugal,
through POCI for financial support. We acknowledge the