steroids 7 1 ( 2 0 0 6 ) 886–894
889
2981, 1370, 1048 cm−1
;
1H NMR (CDCl3) 8.36 (1H, d, J = 4.9 Hz),
2.12.
( )-(8ˇ,9˛,14˛)-3-Aza-11-thia-17˛-vinyl-
1,3,5(10)-trien-13ˇ-ol-11,11-dioxide
N-oxide (23)
8.31 (1H, s), 7.41 (1H, d, J = 4.9 Hz), 5.61 (1H, m), 5.02 (2H, m), 4.02
(1H, d, J = 11.3 Hz), 3.89 (1H, d, J = 10.0 Hz), 3.58 (1H, d, J = 11.3 Hz),
2.82 (2H, m), 2.70 (1H, m), 2.23 (1H, m), 2.01 (1H, m), 1.86 (2H, m),
1.53 (4H, m); 13C NMR (CDCl3) 150.0, 147.1, 145.1, 138.6, 131.1,
119.8, 115.3, 78.8, 78.7, 75.3, 50.5, 49.1, 39.1, 28.5, 25.4, 24.9, 24.8.
HRMS Calcd for C17H21NO2 271.1572, found 271.1574.
Using the same procedure described above for compound 10,
reaction of 0.2 g of 15a [22] and 0.51 g of MCPBA (3 equiv.) gave,
after purification, 0.19 g (85% yield) of 23. mp = 165–166 ◦C; IR
(neat) 3434, 1709, 1269, 743 cm−1 1H NMR (CDCl3) 8.13 (1H,
;
d, J = 1.5 Hz), 8.07 (1H, dd, J = 6.8 Hz, J = 1.5 Hz), 7.92 (1H, d,
J = 6.8 Hz), 5.70 (1H, m), 4.98 (2H, m), 4.51 (1H, d, J = 11.1 Hz),
3.36 (1H, d, J = 13.9 Hz), 3.28 (1H, d, J = 13.9 Hz), 2.75 (2H, m), 2.56
(1H, m), 2.35 (1H, m), 2.11 (1H, m), 1.90 (2H, m), 1.57 (1H, m)
1.41 (3H, m); 13C NMR (CDCl3) 140.0, 138.6, 136.6, 137.9, 125.6,
124.8, 115.8, 78.5, 63.5, 60.4, 55.0, 48.3, 34.7, 27.8, 26.1, 25.0, 24.9.
HRMS Calcd for C17H21NO4S 335.1191, found 335.1193.
2.16.
( )-(8ˇ,9˛,14˛)-3-Aza-11-oxa-17˛-vinyl-
1,3,5(10)-trien-13˛-ol (21b)
IR (neat) 3353, 2982, 1374, 1038 cm−1 1H NMR (CDCl3) 8.37 (1H,
;
d, J = 4.5 Hz), 8.33 (1H, s), 7.45 (1H, d, J = 4.5 Hz), 5.89 (1H, m),
5.15 (2H, m), 4.03 (1H, d, J = 11.2 Hz), 3.97 (1H, d, J = 9.8 Hz), 3.61
(1H, dd, J = 11.2 Hz), 2.79 (2H, m), 2.66 (1H, m), 2.13 (1H, m),
1.92 (3H, m), 1.48 (4H, m); 13C NMR (CDCl3) 149.9, 147.1, 144.9,
138.6, 132.4, 118.4, 114.8, 78.5, 77.2, 75.2, 52.1, 48.9, 39.5, 28.4,
2.13.
( )-(8ˇ,9˛,14˛)-17˛-Acetyl-3-aza-11-thia-
1,3,5(10)-trien-13ˇ-ol-11,11-dioxide
N-oxide (25)
28.0, 25.5, 24.7. HRMS Calcd for C17
271.1574.
H21NO2 271.1572, found
Using the same procedure described above for steroid 11,
reaction of 0.15 g of 23, 10 mg of Pd(OAc)2, 43 mg of benzo-
quinone gave, after purification, 0.1 g (63% yield) of 25 and
17 mg (11% yield) of 26. mp = 173–174 ◦C; IR (neat) 3434, 1709,
2.17.
( )-(8ˇ,9˛,14˛)-3-Aza-11-oxa-17˛-vinyl-
1,3,5(10)-trien-13ˇ-ol N-oxide (24)
Using the same procedure described above for compound 23,
reaction of 80 mg of 21a and 75 mg of MCPBA (1 equiv.) gave,
after purification, 72 mg (83%) of 24. mp = 166–167 ◦C; IR (neat)
1269, 743 cm−1 1H NMR (CDCl3) 8.13 (1H, d, J = 1.7 Hz), 8.07
;
(1H, dd, J = 7.0 Hz, J = 1.7 Hz), 7.89 (1H, d, J = 7.0 Hz), 4.53 (1H, d,
J = 10.9 Hz), 3.64 (1H, d, J = 13.8 Hz), 3.36 (1H, d, J = 13.8 Hz), 3.15
(1H, dd, J = 9.2 Hz, J = 2.5 Hz), 2.74 (2H, m), 2.18 (3H, s), 1.71 (8H,
m); 13C NMR (CDCl3) 210.2, 138.6, 137.8, 136.3, 125.8, 124.9, 78.1,
63.9, 61.9, 59.8, 49.2, 34.4, 32.0, 26.1, 25.3, 25.0, 24.7. HRMS Calcd
for C17H21NO5S 351.114, found 351.11405.
2982, 1693, 1606, 1499, 1264, 1050 cm−1 1H NMR (CDCl3) 7.96
;
(1H, d, J = 7.2 Hz), 7.90 (1H, s), 7.38 (1H, d, J = 7.2 Hz), 5.65 (1H,
m), 5.01 (2H, m), 4.04 (1H, d, J = 11.5 Hz), 3.88 (1H, d, J = 9.8 Hz),
3.52 (1H, dd, J = 11.5 Hz), 2.81 (2H, m), 2.68 (1H, m), 1.83 (2H, m),
1.61 (2H, m), 1.44 (4H, m); 13C NMR (CDCl3) 138.4, 137.2, 136.9,
136.1, 134.6, 124.1, 115.2, 74.2, 73.8, 71.1, 51.4, 48.2, 36.5, 28.9,
26.1, 24.7, 24.2. HRMS Calcd for C17H21NO3 287.1521, found
287.1525.
2.14.
( )-(8ˇ,9˛,14˛)-3-Aza-17˛-(2-oxoethyl)-11-thia-
1,3,5(10)-trien-13ˇ-ol-11,11-dioxide
N-oxide (26)
2.18.
( )-(8ˇ,9˛,14˛)-17˛-Acetyl-3-aza-11-oxa-
Yield: 11%. IR (neat) 3486, 1721, 1611, 1502, 1264, 1125,
1,3,5(10)-trien-13ˇ-ol-11,11-dioxide
N-oxide (27)
745 cm−1
;
1H NMR (CDCl3) 9.62 (1H, s), 8.13 (1H, d, J = 1.7 Hz),
8.08 (1H, dd, J = 7.0 Hz, J = 1.7 Hz), 7.92 (1H, d, J = 7.0 Hz), 4.47 (1H,
d, J = 11.1 Hz), 3.51 (1H, d, J = 13.8 Hz), 3.18 (1H, d, J = 13.8 Hz), 2.74
(2H, m), 2.60 (2H, m), 2.33 (2H, m), 1.81 (7H, m); 13C NMR (CDCl3)
210.8, 138.6, 137.9, 136.4, 125.6, 124.8, 78.3, 63.7, 59.7, 48.8, 48.0,
47.1, 34.7, 28.3, 26.1, 24.9, 24.8. HRMS Calcd for C17H21NO5S
351.114, found 351.11405.
Using the same procedure described above for steroid 25,
reaction of 70 mg of 24, 5 mg of Pd(OAc)2, 21 mg of benzo-
quinone gave, after purification, 58 mg (68% yield) of 27 and
14.5 mg (17% yield) of 28. IR (neat) 3440, 1709, 1270, 743 cm−1
;
1H NMR (CDCl3) 8.01 (1H, d, J = 7.1 Hz), 7.92 (1H, s), 7.39 (1H,
d, J = 7.1 Hz), 4.08 (1H, d, J = 11.6 Hz), 3.95 (1H, d, J = 9.7 Hz), 3.67
(1H, d, J = 11.6 Hz), 3.18 (1H, dd, J = 8.5 Hz, J = 3.3 Hz), 2.82 (2H,
m), 2.19 (3H, s), 1.98 (4H, m), 1.67 (1H, m), 1.53 (3H, m); 13C
NMR (CDCl3) 209.7, 138.4, 137.1, 136.1, 124.2, 80.2, 78.8, 75.5,
58.4, 59.8, 48.2, 39.5, 32.1, 28.9, 26.8, 25.1, 24.9. HRMS Calcd for
2.15.
( )-(8ˇ,9˛,14˛)-3-Aza-11-oxa-17˛-vinyl-
1,3,5(10)-trien-13ˇ-ol (21a)
Under vigorous stirring, a solution of diol 19 (0.2 g, 1.19 mmol)
in DMF (5 mL) was added dropwise at room temperature, to a
solution of KH (5 equiv., 0.06 g, 1.5 mmol) in THF (5 mL). After
1 h, a solution of iodide 5 (0.36 g, 1.3 mmol) in DMF (5 mL) was
added with stirring at 0 ◦C. The mixture was left at this temper-
ature 2 h and then brought at room temperature. The reaction
was monitored by tlc analysis. Crushed ice was added and the
residue was extracted with diethyl ether, and the extracts were
dried over sodium sulfate. The solvent was evaporated and the
crude product was chromatographed on silica gel (petroleum
ether/diethyl ether: 1/1 to 2/8) eluting 144 mg (45% yield) of
steroid 21a and 48 mg (15% yield) of steroid 21b. IR (neat) 3352,
C
17H21NO4 303.1471, found 303.1475.
2.19. )-(8ˇ,9˛,14˛)-3-Aza-11-oxa-17˛-(2-oxoethyl)-
(
1,3,5(10)-trien-13ˇ-ol-11,11-dioxide
N-oxide (28)
Yield: 17%. IR (neat) 3485, 1720, 1612, 1502, 1264, 748 cm−1 1H
;
NMR (CDCl3) 9.69 (1H, s), 8.09 (1H, d, J = 7.2 Hz), 7.98 (1H, s), 7.40
(1H, d, J = 7.2 Hz), 4.07 (1H, d, J = 11.5 Hz), 3.93 (1H, d, J = 9.6 Hz),
3.66 (1H, d, J = 11.5 Hz), 2.80 (2H, m), 2.41 (2H, m), 2.17 (2H, m),
1.80 (7H, m); 13C NMR (CDCl3) 201.1, 138.8, 137.5, 136.3, 125.8,