1204
B.-L. Zhang et al. / Steroids 78 (2013) 1200–1208
42.71, 42.30, 37.15, 36.87, 34.21, 31.64, 31.27, 30.58, 28.29, 20.55,
19.39, 17.14. HRMS (ESI): m/z calcd for C29H35N2OS (M + H)+,
459.2470; found, 459.2478.
30.57, 29.71, 28.32, 20.56, 19.39, 17.07. HRMS (ESI): m/z calcd for
C31H40N3O2S (M + H)+, 518.2841; found, 518.2838.
2.8.2. Reductive products 14a-l
2.8.2.1. Compound 14a. Pale yellow solid, mp 101.1–102.1 °C, 1H
NMR (400 MHz, CDCl3) d 7.38 (m, 5H, –Ph), 5.57 (s, 1H, –NH–),
5.40 (d, 1H, J = 5.42 Hz, 6-H), 4.43 (s, 2H, –CH2– next to amino),
2.8.1.7. Compound 13g. Yellow solid, mp 237.1–238.1 °C, 1H NMR
(400 MHz, CDCl3) d 12.27 (s, 1H, –OH), 9.14 (s, 1H, imine olefinic
–N@CH–), 7.45 (t, 1H, –Ph), 7.42 (d, 1H, –Ph), 7.04 (d, 1H, –Ph),
3.56 (m, 1H, 3a-H), 1.09 (s, 3H, 18-Me), 0.95 (s, 3H, 18-Me). 13C
6.97 (t, 1H, –Ph), 5.42 (d, 1H, J = 5.42 Hz, 6-H), 3.57 (m, 1H, 3a-
NMR (101 MHz, CDCl3) d 173.06, 165.90, 141.28, 137.70, 128.71,
127.70, 127.61, 121.13, 118.35, 71.70, 59.83, 50.77, 49.84, 42.56,
42.31, 37.14, 36.86, 34.28, 31.65, 31.30, 30.46, 27.79, 20.58,
19.37, 16.70. HRMS (ESI): m/z calcd for C27H35N2OS (M + H)+,
435.2470; found, 435.2473.
H), 1.12 (s, 3H, 18-Me), 1.04 (s, 3H, 19-Me). 13C NMR (101 MHz,
CDCl3) d 171.40, 169.16, 162.78, 161.29, 141.35, 134.18, 133.36,
131.93, 120.91, 119.57, 118.70, 117.41, 71.65, 60.01, 50.67, 42.78,
42.29, 37.14, 36.86, 34.20, 31.63, 31.24, 30.57, 28.22, 20.54,
19.39, 17.20. HRMS (ESI): m/z calcd for C27H33N2O2S (M + H)+,
449.2263; found, 449.2264.
2.8.2.2. Compound 14b. White solid, mp 99.5–100.5 °C, 1H NMR
(400 MHz, CDCl3) d 7.32 (s, 4H, –Ph), 6.05 (s, 1H, –NH–), 5.40 (d,
1H, J = 5.42 Hz, 6-H), 4.41 (s, 2H, –CH2– next to amino), 3.55 (m,
2.8.1.8. Compound 13h. Yellow solid, mp 131.9–132.9 °C, 1H NMR
(400 MHz, CDCl3) d 8.63 (s, 1H, imine olefinic –N@CH–), 7.08 (s,
1H, H of pyrrole), 6.82 (s, 1H, H of pyrrole), 6.36 (s, 1H, H of pyr-
1H, 3a-H), 1.08 (s, 3H, 18-Me), 0.93 (s, 3H, 18-Me). 13C NMR
(101 MHz, CDCl3)
d
173.51, 165.63, 141.40, 136.50, 133.26,
role), 5.42 (d, 1H, J = 5.42 Hz, 6-H), 3.58 (m, 1H, 3a-H), 1.11 (s,
128.84, 128.75, 120.94, 118.01, 71.43, 59.77, 50.74, 48.97, 42.54,
42.29, 37.16, 36.84, 34.29, 31.59, 31.27, 30.43, 27.73, 20.54,
19.36, 16.71.HRMS (ESI): m/z calcd for C27H34ClN2OS (M + H)+,
469.2080; found, 469.2078.
3H, 18-Me), 1.02 (s, 3H, 19-Me) 13C NMR (101 MHz, CDCl3) d
174.74, 168.48, 149.68, 141.37, 130.06, 129.07, 124.76, 120.98,
119.13, 111.46, 71.68, 59.90, 50.76, 42.68, 42.31, 37.15, 36.88,
34.22, 31.65, 31.29, 30.56, 28.31, 20.55, 19.39, 17.06. HRMS (ESI):
m/z calcd for C25H32N3OS (M + H)+, 422.2266; found, 422.2263.
2.8.2.3. Compound 14c. White solid, mp 95.1–96.1 °C, 1H NMR
(400 MHz, CDCl3) d 7.39 (d, 1H, 5-H of furan), 6.35 (d, 1H, 3-H of
furan), 6.31 (d d, 1H, 4-H of furan), 5.41 (d, 1H, J = 5.42 Hz, 6-H),
5.36 (s, 1H, –NH–), 4.44 (s, 2H, –CH2– next to amino), 3.56 (m,
2.8.1.9. Compound 13i. Yellow solid, mp 233.1–234.1 °C, 1H NMR
(400 MHz, CDCl3) d 8.88 (s, 1H, imine olefinic –N@CH–), 7.91 (d,
2H, –Ph), 7.35 (d, 2H, –Ph), 5.41 (d, 1H, J = 5.42 Hz, 6-H), 3.56 (m,
1H, 3a-H), 1.09 (s, 3H, 18-Me), 0.95 (s, 3H, 19-Me). 13C NMR
1H, 3a-H), 1.30 (d, 6-H, 2-CH3 of isopropyl), 1.10 (s, 3H, 18-Me),
(101 MHz, CDCl3)
d
172.37, 165.92, 151.07, 142.32, 141.30,
1.03 (s, 3H, 19-Me). 13C NMR (101 MHz, CDCl3) d 174.61, 168.89,
161.05, 153.87, 141.39, 133.05, 130.60, 129.79(2C), 127.04(2C),
120.93, 71.61, 59.94, 50.73, 42.73, 42.30, 37.15, 36.87, 34.34,
34.23, 31.63, 31.28, 30.57, 28.31, 23.72(2C), 20.55, 19.39, 17.11.
HRMS (ESI): m/z calcd for C30H39N2OS (M + H)+, 475.2783; found,
475.2786.
121.10, 118.75, 110.39, 107.77, 71.68, 59.84, 50.78, 42.73, 42.57,
42.31, 37.15, 36.86, 34.27, 31.64, 31.29, 30.47, 27.77, 20.57,
19.37, 16.66. HRMS (ESI): m/z calcd for C25H33N2O2S (M + H)+,
424.2263; found, 2267.
2.8.2.4. Compound 14d. Pale white solid, mp 127.8–128.8 °C, 1H
NMR (400 MHz, DMSO) d 8.13 (d, 1H, H of naphthalene), 7.93 (t,
2H, H of naphthalene), 7.878.04 (d, 1H, H of naphthalene), 7.55
(m, 3H, H of naphthalene), 7.47 (s, 1H, –NH–), 5.31 (d, 1H,
J = 5.42 Hz, 6-H), 4.87 (s, 2H, –CH2– next to amino), 4.64 (d, 1H,
2.8.1.10. Compound 13j. Yellow solid, mp 113.1–114.1 °C, 1H NMR
(400 MHz, CDCl3) d 8.96 (s, 1H, imine olefinic –N@CH–), 8.73 (d,
1H, H of pyridine), 8.29 (d, 1H, H of pyridine), 7.81 (t, 1H, H of pyr-
idine), 7.39 (t, 1H, H of pyridine), 5.39 (d, 1H, J = 5.42 Hz, 6-H), 3.55
3-OH), 3.29 (m, 1H, 3
a-H), 1.00 (s, 3H, 18-Me), 0.85 (s, 3H, 19-
(m, 1H, 3a-H), 1.09 (s, 3H, 18-Me), 1.03 (s, 3H, 19-Me). 13C NMR
Me). 13C NMR (101 MHz, DMSO)
d
171.85, 165.31, 141.63,
(101 MHz, CDCl3)
d
173.11, 169.60, 161.26, 153.78, 149.93,
134.35, 133.33, 131.07, 128.45, 127.65, 126.13, 125.75, 125.72,
125.35, 123.72, 120.08, 116.14, 70.00, 59.09, 50.30, 45.90, 42.29,
42.00, 39.52, 36.80, 36.40, 34.18, 31.45, 30.71, 30.02, 27.22,
141.41, 136.75, 132.27, 125.63, 122.74, 120.84, 71.56, 59.98,
50.71, 42.69, 42.28, 37.14, 36.86, 34.14, 31.62, 31.25, 30.57,
28.37, 20.51, 19.38, 17.13. HRMS (ESI): m/z calcd for C26H32N3OS
(M + H)+, 434.2266; found, 434.2262.
20.16, 19.06, 16.59. HRMS (ESI): m/z calcd for
C31H37N2OS
(M + H)+, 485.2627; found, 485.2622.
2.8.1.11. Compound 13k. Yellow solid, mp 234.9–235.9 °C, 1H NMR
(400 MHz, CDCl3) d 9.08 (s, 1H, imine olefinic –N@CH–), 7.60 (s, 1H,
H of thiophene), 7.59 (s, 1H, H of thiophene), 7.16 (s, 1H, H of thi-
2.8.2.5. Compound 14e. White solid, mp 68.1–69.1 °C, 1H NMR
(400 MHz, CDCl3) d 7.25 (m, 1H, H of Ph), 6.94 (m, 2H, H of Ph),
6.83 (d d, 1H, H of Ph), 5.37 (d, 1H, J = 5.42 Hz, 6-H), 4.37 (s, 2H,
ophene), 5.41 (d, 1H, J = 5.42 Hz, 6-H), 3.56 (m, 1H, 3a-H), 1.11 (s,
–CH2– next to amino), 3.78 (s, 3H, –CH3), 3.52 (m, 1H, 3a-H),
3H, 18-Me), 1.02 (s, 3H, 19-Me). 13C NMR (101 MHz, CDCl3) d
173.89, 168.92, 153.40, 141.90, 141.36, 134.18, 132.18, 131.14,
128.17, 120.95, 71.64, 59.91, 50.72, 42.72, 42.30, 37.15, 36.87,
34.22, 31.63, 31.27, 30.57, 28.30, 20.55, 19.39, 17.12. HRMS (ESI):
m/z calcd for C25H31N2OS2 (M + H)+, 439.1878; found, 439.1869.
1.06 (s, 3H, 18-Me), 0.92 (s, 3H, 19-Me). 13C NMR (101 MHz,
CDCl3) d 173.69, 165.31, 159.86, 141.39, 139.36, 129.65, 120.97,
119.78, 117.90, 113.13, 112.98, 71.51, 59.80, 55.20, 50.76, 49.72,
42.56, 41.96, 37.16, 36.85, 34.24, 31.59, 30.44, 27.77, 27.00,
24.97, 19.35, 16.67. HRMS (ESI): m/z calcd for C28H37N2O2S
(M + H)+, 465.2576; found, 465.2572.
2.8.1.12. Compound 13l. Yellow solid, mp 257.5–258.5 °C, 1H NMR
(400 MHz, CDCl3) d 8.78 (s, 1H, imine olefinic –N@CH–), 7.89 (d,
2H, –Ph), 6.95 (d, 2H, –Ph), 5.43 (d, 1H, J = 5.42 Hz, 6-H), 3.88 (t,
2.8.2.6. Compound 14f. solid, mp 124.9–125.9 °C, 1H NMR
(400 MHz, CDCl3) d 7.30–7.45 (m, 5H, H of –Ph), 6.68 (m, 1H, –
CH@CH–), 6.31 (d, 1H, –CH@CH–), 5.42 (d, 1H, J = 5.42 Hz, 6-H),
5.28 (s, 1H, –NH–), 4.05 (s, 2H, –CH2– next to amino), 3.56 (m,
4H, H of morpholine), 3.57 (m, 1H, 3a-H), 3.34 (t, 4H, H of morpho-
line), 1.11 (s, 3H, 18-Me), 1.03 (s, 3H, 19-Me). 13C NMR (101 MHz,
CDCl3) d 175.28, 168.58, 160.54, 153.83, 141.34, 131.41(2C),
129.48, 126.08, 121.02, 114.06(2C), 71.69, 66.61(2C), 59.90,
50.75, 47.61(2C), 42.71, 42.31, 37.14, 36.87, 34.25, 31.65, 31.29,
1H, 3
(101 MHz, CDCl3)
128.61, 127.43, 126.72, 126.15, 120.08, 116.15, 69.98, 59.09,
a-H), 1.10 (s, 3H, 18-Me), 0.96 (s, 3H, 19-Me). 13C NMR
d
171.92, 165.40, 141.66, 136.55, 130.67,