9042
G. Li et al. / Tetrahedron 64 (2008) 9033–9043
3.1.14. 9,9-Diphenyl-9H-fluorene (15)
1H NMR (CDCl3, Me4Si):
d
4.75 (s, 1H), 4.89 (ABq, J¼16.2 Hz, 1H),
Purification of the crude product by flash chromatography on
silica gel (eluent: petroleum ether/ethyl acetate¼10:1) afforded the
title compound as a white solid in 86% yield. Mp 223–225 ꢁC (lit.21
5.24 (ABq, J¼15.9 Hz, 1H), 6.88–6.91 (m, 2H), 6.97–7.11 (m, 4H),
7.19–7.33 (m, 10H), 7.66 (d, J¼7.5 Hz, 1H), 7.94 (d, J¼8.1 Hz, 1H); 13
C
NMR (CDCl3, Me4Si):
d 47.9, 49.0, 110.5, 118.4, 119.7, 120.3, 120.6,
224 ꢁC); 1H NMR (CDCl3, Me4Si):
d
7.16–7.25 (m, 12H), 7.32 (td,
121.5, 121.9, 123.0, 124.6, 126.5, 127.2, 127.4, 128.1, 128.6, 128.8,
136.7, 138.5, 139.0, 141.2, 148.7, 151.1; IR (KBr): 3056, 3030, 2923,
2852, 1604, 1525, 1495, 1470, 1454, 1445, 1432, 1342, 746, 727,
696 cmꢀ1. Anal. Calcd for C28H21N: C, 90.53; H, 5.70; N, 3.77. Found:
C, 90.50; H, 5.84; N, 3.74.
J¼6.9, 1.5 Hz, 2H), 7.40 (d, J¼7.2 Hz, 2H), 7.73 (d, J¼7.5 Hz, 2H); 13C
NMR (CDCl3, Me4Si):
d 65.4, 120.1, 126.1, 126.6, 127.4, 127.7, 128.1,
128.2, 140.1, 145.9, 151.1; IR (KBr): 3051, 3017, 2926, 1594, 1489,
1447, 1031, 912, 755, 741, 728, 627 cmꢀ1
.
3.1.15. 8-Phenyl-8H-3-thia-cyclopenta[a]indene (16a)
3.1.20. 5-Benzyl-6-naphthalen-1-yl-5,6-dihydro-indeno[2,1-b]-
indole (17b)
Purification by flash chromatography on silica gel (eluent:
dichloromethane) afforded the title compound as a white solid as
a mixture of two rotamers with a ratio of 44:56 by 1H NMR in 96%
Purification of the crude product by preparative TLC (solution:
petroleum ether/ethyl acetate¼20:1) afforded the title compound
as a white solid in 84% NMR yield (from the alcohol 5a) or 69% yield
(from the ester 6a). Mp 136 ꢁC; 1H NMR (CDCl3, Me4Si):
d 4.84 (s,
1H), 6.90 (d, J¼5.1 Hz, 2H), 7.07–7.12 (m, 3H), 7.18–7.28 (m, 6H), 7.45
yield. 1H NMR (CDCl3, Me4Si):
d
4.65 (ABq, J¼16.5 Hz, 1H), 4.71
(d, J¼7.8 Hz, 1H); 13C NMR (CDCl3, Me4Si):
d
51.6, 118.8, 122.5, 125.1,
(ABq, J¼16.2 Hz, 1H), 4.97 (ABq, J¼16.5 Hz, 1H), 5.02 (s, 1H), 5.10
(ABq, J¼16.2 Hz, 1H), 5.58 (s, 1H), 6.61 (d, J¼7.2 Hz), 6.67 (d,
J¼7.2 Hz), 6.81–7.43 (m), 7.51–7.59 (m), 7.64–7.73 (m), 7.78 (d,
J¼7.2 Hz, 1H), 7.86–7.89 (m), 7.97 (d, J¼7.5 Hz, 1H), 8.01 (d, J¼7.5 Hz,
125.3,126.9,127.3,127.6,127.8,128.7,137.9,140.2,142.7, 150.7,151.8;
IR (KBr): 3096, 3075, 3018, 2918, 1602, 1493, 1452, 1341, 1283, 1290,
1072, 823, 752, 699 cmꢀ1; HRMS (EI) for C17H12S: calcd 248.0660,
found 248.0662. Anal. Calcd for C17H12S: C, 82.22; H, 4.87. Found: C,
82.39; H, 5.00.
1H), 8.28 (d, J¼7.8 Hz, 1H); 13C NMR (CDCl3, Me4Si):
d 43.5, 47.7,
48.2, 50.8, 110.5, 110.6, 118.6, 118.7, 119.57, 119.63, 119.8, 120.3, 120.4,
121.3, 121.4, 121.5, 122.0, 122.1, 122.9, 123.0, 123.5, 124.0, 124.1,
124.2, 124.4, 125.1, 125.6, 125.7, 125.8, 126.2, 126.3, 126.3, 126.6,
127.1, 127.4,127.4, 127.5, 127.6, 128.2,128.3,128.4,128.8,129.1, 129.9,
131.4,132.3,133.4,134.1,134.2,134.7,136.4,136.5,138.4,138.8,141.3,
141.4, 147.7, 148.8, 151.0, 151.4; IR (KBr): 3.57, 3041, 3004, 2924,
1599, 1528, 1492, 1478, 1448, 1461, 1392, 1339, 1145, 800, 774, 748,
732, 720 cmꢀ1; HRMS (EI) for C32H23N: calcd 421.1830, found
421.1833. Anal. Calcd for C32H23N: C, 91.18; H, 5.50; N, 3.32. Found:
C, 90.92; H, 5.23; N, 3.07.
3.1.16. 2-Chloro-8-phenyl-8H-3-thia-cyclopenta[a]indene (16b)
Purification of the crude product by preparative TLC (solution:
petroleum ether/ethyl acetate¼20:1) afforded the title compound
as a brown solid in 82%. Mp 106 ꢁC; 1H NMR (CDCl3, Me4Si):
d 4.78
(s, 1H), 6.78 (s, 1H), 7.04–7.15 (m, 3H), 7.20–7.28 (m, 5H), 7.36 (d,
J¼7.5 Hz, 1H); 13C NMR (CDCl3, Me4Si):
d 52.5, 118.6, 122.2, 125.0,
125.5,127.1,127.4,127.7,128.8,131.3,137.6,139.4,139.9,149.2,149.5;
IR (KBr): 3084, 3062, 3020, 2915, 1601, 1510, 1494, 1458, 1451, 1341,
1018, 953, 819, 755, 713, 698 cmꢀ1; HRMS (EI) for C17H11ClS: calcd
282.0270, found 282.0260.
3.1.21. 5-Benzyl-6-(6-methoxy-naphthalen-2-yl)-5,6-dihydro-
indeno[2,1-b]indole (17c)
3.1.17. 10-Phenyl-10H-9-thia-indeno[1,2-a]indene (16c)
Purification by flash chromatography on silica gel (eluent:
dichloromethane) afforded the title compound as a white solid in
73% yield (from the alcohol 10c with TfOH as catalyst) or 89% yield
(from the ester 11c with BF3$Et2O as catalyst). Mp 222–224 ꢁC; 1H
Purification of the crude product by flash chromatography on
silica gel (eluent: petroleum ether/ethyl acetate¼10:1) afforded the
title compound as a white solid in 90% yield. Mp 136–138 ꢁC; 1H
NMR (CDCl3, Me4Si):
d
5.11 (s, 1H), 7.13–7.40 (m, 9H), 7.48 (td, J¼7.8,
NMR (CDCl3, Me4Si):
d
3.86 (s, 3H), 4.84 (ABq, J¼15.9 Hz, 1H), 4.85
1.2 Hz, 1H), 7.84 (d, J¼7.8 Hz, 2H), 8.19 (d, J¼7.8 Hz, 1H); 13C NMR
(s, 1H), 5.16 (ABq, J¼16.5 Hz, 1H), 6.83–6.88 (m, 3H), 6.96 (t,
J¼8.4 Hz, 1H), 7.04–7.32 (m, 10H), 7.50 (d, J¼8.4 Hz, 1H), 7.58 (s, 1H),
7.61 (d, J¼9.0 Hz, 1H), 7.68 (d, J¼7.5 Hz, 1H), 7.96 (d, J¼7.5 Hz, 1H);
(CDCl3, Me4Si): d 52.8, 119.1, 122.1, 123.8, 124.0, 124.7, 124.8, 1245.9,
127.2,127.3,127.8,128.8,132.8,138.5,139.9,140.1,145.1,150.9,151.2;
IR (KBr): 3060, 3025, 2897, 1602, 1494, 1479, 1452, 1423, 1389, 1176,
1055, 1012, 934, 770, 729 cmꢀ1. Anal. Calcd for C21H14S: C, 84.53; H,
4.73. Found: C, 84.52; H, 4.78.
13C NMR (CDCl3, Me4Si):
d 47.9, 49.0, 55.3, 105.7, 110.5, 118.4, 118.9,
119.7, 120.4, 120.7, 121.5, 121.9, 123.0, 124.7, 126.2, 126.5, 127.1, 127.4,
127.5, 127.6, 128.5, 129.0, 133.6, 133.9, 136.7, 139.1, 141.2, 148.7, 151.2,
157.6; IR (KBr): 3056, 3028, 2962, 2935, 1634, 1606, 1519, 1493,
3.1.18. 10-(4-Vinyl-phenyl)-10H-9-thia-indeno[1,2-a]indene (16d)
Purification of the crude product by flash chromatography on
silica gel (eluent: petroleum ether/ethyl acetate¼10:1) afforded the
title compound as a white solid in 87% yield. Mp 149–151 ꢁC; 1H
1470, 1459, 1448, 1256, 1208, 1163, 1209, 859, 839, 812, 738 cmꢀ1
;
HRMS (EI) for C33H25NO: calcd 451.1936, found 451.1925. Anal.
Calcd for C33H25NO: C, 87.77; H, 5.58; N, 3.10. Found: C, 87.95; H,
5.79; N, 3.24.
NMR (CDCl3, Me4Si):
d
5.05 (s, 1H), 5.18 (d, J¼10.8 Hz, 1H), 5.67 (d,
J¼17.7 Hz, 1H), 6.64 (dd, J¼17.4, 10.8 Hz, 1H), 7.06–7.16 (m, 3H),
7.24–7.38 (m, 5H), 7.46 (t, J¼7.8 Hz, 1H), 7.82 (d, J¼7.8 Hz, 2H), 8.16
3.1.22. 6-Benzo[b]thien-3-yl-5-benzyl-5,6-dihydro-indeno[2,1-b]-
indole (17d)
(d, J¼7.8 Hz, 1H); 13C NMR (CDCl3, Me4Si):
d
52.5, 113.7, 119.1, 122.1,
Purification by flash chromatography on silica gel (eluent:
dichloromethane) afforded the title compound as a white solid in
123.8, 124.1, 124.7, 124.9, 126.7, 127.3, 128.0, 132.8, 136.3, 136.6,
138.5, 139.5, 140.1, 145.1, 150.8, 151.2; IR (KBr): 3062, 1629, 1600,
1508, 1482, 1427, 1405, 1200, 1177, 1016, 992, 913, 852, 805, 766,
724 cmꢀ1; HRMS (EI) for C23H16S: calcd 324.0973, found 324.0974.
Anal. Calcd for C23H16S: C, 85.15; H, 4.97. Found: C, 85.42; H, 4.74.
99% yield. Mp 184–185 ꢁC; 1H NMR (CDCl3, Me4Si):
d 4.79 (ABq,
J¼16.2 Hz, 1H), 5.05 (s, 1H), 5.08 (ABq, J¼17.7 Hz, 1H), 6.62–7.33 (m,
15H), 7.71 (d, J¼6.6 Hz, 2H), 7.98 (d, J¼8.1 Hz, 1H); 13C NMR (CDCl3,
Me4Si):
d 44.7 (br), 47.7 (br), 110.5, 118.5, 119.7, 120.4, 1120.6 (br),
121.6, 121.9, 122.5 (br), 123.0, 124.2, 124.3, 125.6 (br), 126.2, 127.2,
127.5 (br), 127.7, 128.3, 131.6 (br), 136.4, 136.7 (br), 138.9 (br), 140.7,
141.3, 145.8 (br), 149.1 (br); IR (KBr): 3060, 2925, 2875, 1604, 1521,
1495, 1459, 1440, 1425, 1263, 1162, 740, 723, 702 cmꢀ1; HRMS (EI)
for C30H21NS: calcd 427.1395, found 427.1386. Anal. Calcd for
3.1.19. 5-Benzyl-6-phenyl-5,6-dihydro-indeno[2,1-b]indole (17a)
Purification by flash chromatography on silica gel (eluent: pe-
troleum ether/ethyl acetate¼10:1) afforded the title compound as
a light yellow solid in 83% (from the alcohol 10a with TfOH as
catalyst), or 91% (from the ester 11a with TfOH as catalyst), or 90%
yield (from the ester 11a with BF3$Et2O as catalyst). Mp 194–196 ꢁC;
C30H21NS: C, 84.27; H, 4.95; N, 3.28. Found: C, 84.03; H, 5.04;
N, 3.04.