7256
X. Wu et al. / Tetrahedron 67 (2011) 7251e7257
hexaneeisopropanol¼4:1, flow rate¼0.5 mL/min,
l
¼220 nm):
ADH, hexaneeisopropanol¼4:1, flow rate¼0.5 mL/min, ¼220 nm):
l
tR¼29.89 min (major enantiomer), tR¼41.95 min (minor
tR¼12.34 min (major enantiomer), tR¼9.66 min (minor
enantiomer).
enantiomer).
4.2.14. (13R,11bS)-3,3-Dimethyl-13-ethyl-2,3,4,5,6,11b,12,13-
4.2.18. (12R,10bS)-12-Propyl-2,3,4,5,10b,11,12-heptahydro-1-oxo-
octahydro-1-oxo-11H-4b,11-diazaindeno[2,1-
a
]phenanthrene
10.98 (br, 1H),
10H-3b,10-diazaindeno[2,1-
a
]cyclopenta[
a
]phenanthrene
(8n). Yellow solid; 1H NMR (DMSO-d6, 400 MHz):
d
(8r). Yellow solid; 1H NMR (DMSO-d6, 400 MHz):
d 11.04 (br, 1H), 7.42
7.41 (d, J¼7.6 Hz, 1H), 7.32 (d, J¼7.6 Hz, 1H), 7.06 (t, J¼7.6 Hz, 1H),
6.98 (t, J¼7.6 Hz, 1H), 4.63 (d, J¼11.2 Hz, 1H), 4.23 (d, J¼12.6 Hz, 1H),
3.14e3.21 (m, 1H), 2.73e2.79 (m, 3H), 2.62 (d, J¼11.6 Hz, 1H),
2.52e2.562 (m, 1H), 2.33 (d, J¼16.3 Hz, 1H), 2.12 (d, J¼15.5 Hz, 1H),
1.93 (d, J¼15.5 Hz, 1H), 1.48e1.58 (m, 1H), 1.36 (td, J¼12.7 Hz and
4.6 Hz, 1H), 1.21e1.28 (m, 1H), 1.05 (s, 3H), 0.94e1.00 (m, 6H); 13C
(d, J¼8.0 Hz, 1H), 7.33 (d, J¼8.0 Hz, 1H), 7.07 (t, J¼8.0 Hz, 1H), 6.98 (t,
J¼8.0 Hz, 1H), 4.64 (d, J¼11.2 Hz, 1H), 4.03 (d, J¼12.8 Hz, 1H), 3.44e3.46
(m, 1H), 2.74e2.83 (m, 2H), 2.62e2.71 (m, 2H), 2.50e2.53 (m, 1H),
2.11e2.25 (m, 2H), 1.16e1.64 (m, 6H), 0.94 (t, J¼6.8 Hz, 3H); 13C NMR
(DMSO-d6,100 MHz) d 198.5,170.5,136.1,133.6,126.3,120.9,118.5,117.6,
112.5, 110.9, 106.6, 49.4, 43.8, 37.3, 32.9, 31.6, 27.6, 24.4, 21.2, 19.7, 14.1;
NMR (DMSO-d6, 100 MHz)
d
192.0, 156.2, 136.5, 135.4, 126.8, 121.3,
½
a 2D5
ꢂ
ꢀ36.08 (c 0.20, CH3OH); HRMS (ESI) calcd for (C21H24N2ONa)þ
119.0, 118.0, 111.5, 109.2, 107.4, 50.3, 49.9, 44.9, 32.5, 30.3, 30.2, 29.7,
343.1781, found 343.1787; HPLC (Daicel Chiralpak ODH,
27.3, 27.2, 22.5, 12.2; ½a D25
ꢂ
ꢀ82.56 (c 0.50, CHCl3); HRMS (ESI) calcd
hexaneeisopropanol¼4:1, flow rate¼0.7 mL/min,
l
¼220 nm):
for (C23H28N2ONa)þ 371.2094, found 371.2104; HPLC (Daicel Chir-
tR¼14.98 min (major enantiomer), tR¼25.09 min (minor enantiomer).
alpak ASH, hexaneesopropanol¼9:1, flow rate¼0.6 mL/min,
l
¼220 nm): tR¼51.24 min (major enantiomer), tR¼78.43 min (mi-
4.2.19. (13R,11bS)-13-Propyl-8-methyl-2,3,4,5,6,11b,12,13-octahydro-
nor enantiomer).
1-oxo-11H-4b,11-diazaindeno[2,1-
a]phenanthrene (8s). White solid;
1H NMR (CDCl3, 400 MHz,):
d
8.28 (br,1H), 7.22e7.27 (m, 2H), 6.97 (d,
4.2.15. (13R,11bS)-3,3-Dimethyl-13-propyl-2,3,4,5,6,11b,12,13-
J¼8.0 Hz,1H), 4.62e4.69 (m,1H,), 4.22 (dd, J¼13.2 Hz and 3.2 Hz,1H,),
3.20e3.27 (m,1H,), 3.03e3.08 (m,1H,), 2.81e2.89 (m,1H), 2.74e2.81
(m,1H), 2.58e2.66 (m,1H), 2.47e2.53 (m,1H), 2.44 (s, 3H), 2.37e2.39
(m, 1H), 2.30e2.36 (m, 2H), 1.91e2.06 (m, 2H,), 1.56e1.65 (m, 2H),
1.32e1.44 (m, 1H), 1.22e1.29 (m, 2H), 0.94 (t, J¼7.2 Hz, 3H); 13C NMR
octahydro-1-oxo-11H-4b,11-diazaindeno[2,1-
a
]phenanthrene
10.97 (br, 1H),
(8o). Yellow solid; 1H NMR (DMSO-d6, 400 MHz):
d
7.39 (d, J¼7.6 Hz, 1H), 7.31 (d, J¼7.6 Hz, 1H), 7.04 (t, J¼7.6 Hz, 1H),
6.96 (t, J¼7.6 Hz, 1H), 4.64 (d, J¼11.0 Hz, 1H), 4.22 (d, J¼12.6 Hz,
1H), 3.13e3.18 (m, 1H), 2.84 (s, 1H), 2.68e2.76 (m, 2H), 2.50e2.63
(m, 1H), 2.31 (d, J¼16.4 Hz, 1H), 2.09 (d, J¼15.6 Hz, 1H), 1.94 (t,
J¼15.6 Hz, 1H), 1.54e1.58 (m, 1H), 1.22e1.45 (m, 4H), 1.04 (s, 3H),
(CDCl3,100 MHz): d 194.0, 158.0, 134.7, 134.5, 129.1, 127.2, 123.6, 117.9,
111.7,110.9,108.1, 50.5, 45.2, 36.8, 36.2, 31.2, 27.7, 27.4, 22.6, 22.4, 21.6,
20.6, 14.5; ½a 2D5
ꢀ20.25 (c 1.10, CHCl3); HRMS (ESI) calcd for
ꢂ
0.92 (s, 6H); 13C NMR (DMSO-d6, 100 MHz)
d
191.3, 155.6, 136.0,
(C23H29N2O)þ 349.2274, found 349.2287; HPLC conditions: AD-H
column, hexaneeisopropanol¼4:1, flow rate¼0.7 mL/min,
tR¼12.24 min (majorenantiomer), tR¼24.25min(minorenantiomer).
134.9, 126.3, 120.7, 118.5, 117.5, 111.0, 108.7, 106.8, 79.1, 49.8, 49.3,
44.4, 36.3, 32.0, 30.3, 29.7, 27.1, 26.8, 22.0, 19.8, 14.1; ½a D25
ꢀ78.99
ꢂ
(c 0.60, CHCl3); HRMS (ESI) calcd for (C24H31N2O)þ 363.2431,
found
363.2437;
HPLC
(Daicel
Chiralpak
ASH,
4.2.20. (13R,11bS)-2,2-Dimethyl-13-propyl-2,3,4,5,6,11b,12,13-
hexaneeisopropanol¼9:1, flow rate¼0.6 mL/min,
l
¼220 nm):
octahydro-1-oxo-11H-4b,11-diazaindeno[2,1-
a]phenanthrene
tR¼38.38 min (major enantiomer), tR¼61.97 min (minor
(8t). Yellow solid; 1H NMR (CDCl3, 400 MHz):
d
8.18 (br,1H), 7.48 (d,
enantiomer).
J¼8.0 Hz,1H), 7.34 (d, J¼8.0 Hz,1H), 7.07e7.19 (m, 2H), 4.60e4.68 (m,
1H), 4.20e4.50 (dd, J¼13.2 Hz and 3.6 Hz, 1H), 3.13e3.20 (m, 1H),
2.96e2.30 (m,1H), 2.72e2.86 (m, 2H), 2.58e2.64 (m,1H), 2.42e2.48
(m, 1H), 2.30e2.38 (m, 1H), 1.72e1.81 (m, 2H), 1.53e1.61 (m, 1H),
1.42e1.49 (m, 2H), 1.27e1.32 (m, 1H), 1.12e1.19 (m, 1H), 1.07 (s, 3H),
4.2.16. (13R,11bS)-3,3-Dimethyl-13-pentyl-2,3,4,5,6,11b,12,13-
octahydro-1-oxo-11H-4b,11-diazaindeno[2,1-
a
]phenanthrene
10.97 (br, 1H),
(8p). Yellow solid; 1H NMR (DMSO-d6, 400 MHz):
d
7.40 (d, J¼8.0 Hz, 1H), 7.32 (d, J¼8.0 Hz, 1H), 7.05 (t, J¼8.0 Hz, 1H),
6.97 (t, J¼8.0 Hz, 1H), 4.64 (d, J¼11.2 Hz, 1H), 4.24 (d, J¼12.4 Hz, 1H),
3.14e3.21 (m, 1H), 2.56e2.81 (m, 4H), 2.32 (d, J¼16.0 Hz, 1H), 2.10
(d, J¼16.0 Hz,1H),1.92 (d, J¼16.0 Hz,1H),1.23e1.55 (m,10H),1.05 (s,
1.03 (s, 3H), 0.87 (t, J¼7.2 Hz, 3H); 13C NMR (CDCl3,100 MHz):
d 199.2,
155.8, 136.3, 134.5, 126.9, 122.1, 119.8, 118.1, 111.2, 109.6, 108.6, 50.1,
44.6, 38.4, 37.0, 35.9, 31.4, 27.9, 25.7, 24.9, 24.2, 22.6, 20.7, 14.2; ½a D25
ꢂ
ꢀ46.59 (c 0.85, CHCl3); HRMS (ESI) calcd for (C24H31N2O)þ 363.2431,
3H), 0.89e0.94 (m, 6H); 13C NMR (DMSO-d6, 100 MHz)
d
191.3,
found
363.2432;
HPLC
conditions:
AD-H
column,
155.6, 136.0, 134.8, 126.3, 120.7, 118.4, 117.5, 111.0, 108.7, 106.8, 49.8,
49.3, 44.4, 33.9, 32.0, 31.4, 30.2, 29.6, 27.2, 26.8, 26.2, 22.1, 22.0,14.0;
hexaneeisopropanol¼4:1, flow rate¼0.7 mL/min, tR¼9.21 min
(major enantiomer), tR¼11.31 min (minor enantiomer).
½
a 2D5
ꢂ
ꢀ117.02 (c 0.35, CHCl3); HRMS (ESI) calcd for (C26H35N2O)þ
391.2744, found 391.2751; HPLC (Daicel Chiralpak ADH,
4. 2. 21. (13S,11bS)-2, 2-Dimethyl-13-(4-bromophenyl)-
hexaneeisopropanol¼4:1, flow rate¼0.5 mL/min,
l
¼220 nm):
2,3,4,5,6,11b,12,13-octahydro-1-oxo-11H-4b,11-diazaindeno[2,1-
a]
tR¼12.39 min (major enantiomer), tR¼9.50 min (minor
phenanthrene (8u). White solid; 1H NMR (CDCl3, 400 MHz):
d
7.77
enantiomer).
(br, 1H), 7.47 (d, J¼7.6 Hz, 1H), 7.38 (d, J¼8.4 Hz, 2H), 7.27 (d,
J¼7.6 Hz, 1H), 7.07e7.18 (m, 2H), 7.04 (d, J¼8.4 Hz, 2H), 4.29e4.33
(m, 3H), 3.20e3.27 (m, 1H), 2.81e2.94 (m, 3H), 2.57e2.66 (m, 1H),
2.29e2.32 (m, 1H), 1.87e2.06 (m, 3H), 1.14 (s, 3H), 1.11 (s, 3H); 13C
4.2.17. (13R,11bS)-3,3-Dimethyl-13-heptyl-2,3,4,5,6,11b,12,13-
octahydro-1-oxo-11H-4b,11-diazaindeno[2,1-
a
]phenanthrene
10.96 (br, 1H),
(8q). Yellow solid; 1H NMR (DMSO-d6, 400 MHz):
d
NMR (CDCl3, 100 MHz): d 198.8, 157.5, 145.4, 136.3, 133.5, 131.6,
7.40 (d, J¼7.6 Hz, 1H), 7.32 (d, J¼7.6 Hz, 1H), 7.05 (t, J¼7.6 Hz, 1H),
6.97 (t, J¼7.6 Hz, 1H), 4.63 (d, J¼11.1 Hz, 1H), 4.24 (d, J¼12.7 Hz, 1H),
3.14e3.21 (m, 1H), 2.52e2.81 (m, 5H), 2.32 (d, J¼16.0 Hz, 1H), 2.10
(d, J¼15.2 Hz,1H),1.92 (d, J¼15.2 Hz,1H),1.23e1.55 (m,13H),1.05 (s,
129.4, 126.9, 122.3, 119.9, 118.2, 111.1, 109.1, 105.9, 49.6, 44.5, 38.5,
36.2, 35.8, 34.4, 25.6, 24.6, 24.5, 22.5; ½a D25
þ58.72 (c 0.40, CHCl3);
ꢂ
HRMS (ESI) calcd for (C27H28BrN2O)þ 475.1380, found 475.1393;
HPLC conditions: AD-H column, hexaneeisopropanol¼4:1, flow
rate¼0.7 mL/min, tR¼20.52 min (major enantiomer), tR¼10.87 min
(minor enantiomer).
3H), 0.86e0.94 (m, 6H); 13C NMR (DMSO-d6, 100 MHz)
d 191.3,
155.6, 136.0, 134.8, 126.3, 120.7, 118.4, 117.5, 111.0, 108.7, 106.8, 49.8,
49.3, 44.4, 33.9, 32.0, 31.3, 30.2, 29.6, 29.2, 28.8, 27.2, 26.8, 26.6,
22.1, 22.0, 13.9; ½a D25
ꢂ
ꢀ63.59 (c 0.55, CHCl3); HRMS (ESI) calcd for
4.2.22. (13R,11bS)-2,2-Dimethyl-13-propyl-8-methoxyl-
2,3,4,5,6,11b,12,13-octahydro-1-oxo-11H-4b,11-diazaindeno[2,1-a]
(C28H39N2O)þ 419.3057, found 419.3071; HPLC (Daicel Chiralpak