N. G. Ramesh et al. / Tetrahedron 58 *2002) 1361±1368
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1
needles. Mp: 1118C; H NMR 6400 MHz, CDCl3) d 6.13
2.20 mmol) was added to a clear solution of 6b 60.243 g,
1.00 mmol) in dichloromethane 620 ml). After one day, the
reaction mixture was extracted with a 25 ml 0.1 M NaOH
solution. The organic phase was concentrated in vacuo and
10b 60.282 g, 90%) was obtained by column chromato-
graphy 6hexane±ethyl acetate1:1). Recrystallisation from
ethyl acetate provided an analytically pure sample of 10b as
6dd, J5.7, 2.8 Hz, 1H), 5.95 6dd, J5.7, 2.9 Hz, 1H), 3.71
6m, 3H), 3.44 6br s, 1H), 3.41 6br s, 1H), 1.88 6br t, 2H),
1.73±1.28 6m, 10H); 13C NMR 6100 MHz, CDCl3) d 200.5,
166.4, 137.1, 134.7, 63.7, 61.7, 50.6, 50.1, 47.2, 45.4, 43.3,
32.6, 32.4, 25.4, 24.5, 24.3; IR 6KBr, cm21): n 3489, 1668,
1446; HRMS/EI: m/z calcd for C16H19NO79Br81Br:
400.9813 6M1). Found: 400.9814 6M1); Anal. calcd for
C16H19NOBr2: C, 47.91; H, 4.77; N, 3.49%. Found: C,
48.06; H, 4.73; N, 3.53%.
1
white needles. Mp: 1778C; H NMR 6400 MHz, CDCl3,
T281 K, ppm) d 6.13 6dd, J5.4, 2.9 Hz, 1H), 5.97
6dd, J5.4, 3.0 Hz, 1H), 5.15 6br d, J10.9 Hz, 0.7H),
3
5.03 6br d, J8.3 Hz, 0.3H), 4.15 6m, 0.3H), 3.94 6m,
4.3.3.
4,N-Dibromo-5-n-pentylamino-endo-tricyclo-
0.7H), 3.33 6br s, 1H), 3.23 6d, J4.0 Hz, 1H), 3.15 6br s,
0.7H), 3.11 6br s, 0.3H), 2.28 6d, J9.1 Hz, 1H), 2.2±1.1 6m,
11H); 13C NMR 6100 MHz, CDCl3, T281 K, ppm) d
189.5, 164.4, 137.4, 132.3, 103.4, 71.4, 61.3, 53.3, 50.3,
43.8, 34.4, 24.8; IR 6KBr, cm21) n 3242, 1674, 1569,
1447; HRMS/EI: m/z calcd for C16H19NO35Cl2: 311.0844
6M1). Found: 311.0844 6M1). Anal. calcd for
C16H19NOCl2: C, 61.55; H, 6.13; N, 4.49%. Found: C,
61.76; H, 6.17; N, 4.50%.
[5.2.1.02,6]deca-4,8-dien-3-one 68c). Compound 8c was
obtained in 97% yield 60.385 g) from 6c 60.234 g,
1.01 mmol) and NBS 60.370 g, 2.08 mmol) in CH2Cl2
610 ml) as a viscous yellow oil. 1H NMR 6400 MHz,
CDCl3, T305 K) d 6.13 6dd, J5.7, 2.8 Hz, 1H), 5.95
6dd, J5.7, 2.9 Hz, 1H), 3.80±3.60 6m, 4H), 3.49 6br s,
1H), 3.44 6br s, 1H), 1.77 6m, 2H), 1.68 6d, J8.9 Hz,
1H), 1.55 6d, J8.9 Hz, 1H), 1.40 6m, 4H), 0.94 6t,
J6.9 Hz, 3H); 13C NMR 6100 MHz, CDCl3, T305 K):
d 199.9, 168.3, 136.7, 134.5, 63.9, 53.4, 50.5, 50.1, 46.3,
45.3, 43.7, 29.9, 29.7, 22.5, 14.0; HRMS/EI: m/z calcd for
C15H19NO79Br2: 386.9833 6M1). Found: 386.9833 6M1).
4.3.7. 4,6-Dibromo-5-pyrrolidino-endo-tricyclo[5.2.1.02,6]-
deca-4,8-dien-3-one 611a). NBS 60.173 g, 0.97 mmol) was
added to a clear solution of 6e 60.101 g, 0.47 mmol) in
CH2Cl2 610 ml). After 10 min, the reaction mixture was
extracted with a 15 ml 0.1 M NaOH solution. The organic
phase was dried over MgSO4 and concentrated in vacuo.
This yielded 11a as a white solid 60.175 g, 99%). Recrys-
tallisation from ethyl acetate provided an analytically pure
4.3.4. 4,N-Dibromo-5-61R,2S,6R,7S,10R)610-phenylethyl-
amino)-endo-tricyclo[5.2.1.02,6]deca-4,8-dien-3-one 68d).
Compound 8d was obtained in 98% yield 60.818 g)
from 6d 60.530 g, 2.0 mmol) and NBS 60.712 g,
1
1
4.0 mmol) in CH2Cl2 610 ml) as a viscous yellow oil. H
sample of 11a as white needles. Mp: 1618C 6D); H NMR
NMR 6300 MHz, CDCl3) d 7.44±7.22 6m, 5H), 5.93
6dd, J5.6, 2.8 Hz, 1H), 5.23 6dd, J5.6, 2.8 Hz, 1H),
5.04 6q, J6.3 Hz, 1H), 3.76 6d, J2.2 Hz, 2H), 3.37 6br s,
1H), 3.31 6br s, 1H), 1.57±1.48 6m, 5H); 13C NMR
675 MHz, CDCl3) d 199.9, 167.1, 144.7, 136.0, 134.8,
128.4, 126.8, 125.8, 64.2, 60.8, 50.3, 50.2, 47.1, 45.3,
43.3, 25.0.
6400 MHz, CDCl3) d 6.12 6dd, J5.6, 2.9 Hz, 1H), 5.98 6dd,
J5.5, 3.0 Hz, 1H), 4.25 6br s, 2H), 3.98 6br s, 2H), 3.45 6d,
J4.1 Hz, 1H), 3.37 6br s, 1H), 3.33 6br s, 1H), 2.26 6br d,
J9.1 Hz, 1H), 1.98 6m, 5H); 13C NMR 6100 MHz, CDCl3,
T305 K, ppm) d 192.0, 165.0, 137.0, 131.6, 94.0, 67.2,
61.3, 54.6, 50.8, 50.1, 45.4, 25.0; IR 6KBr, cm21) n 1669,
1552, 1477, 1456; HRMS/EI: m/z calcd for
C14H15NO79Br81Br: 372.9500 6M1). Found: 372.9494
6M1); Anal. calcd for C14H15NOBr2: C, 45.07; H, 4.05; N,
3.75%. Found: C, 45.40; H, 4.03; N, 3.80%.
4.3.5. 5-Benzylamino-4,6-dichloro-endo-tricyclo[5.2.1.02,6]-
deca-4,8-dien-3-one 610a). NCS 60.124 g, 0.93 mmol) was
added to a clear solution of 6a 60.100 g, 0.40 mmol) in
CH2Cl2 610 ml). After 1 min, a white precipitate started to
form. After one day the reaction mixture was extracted with
0.1 M NaOH 615 ml) solution. The organicphase was
concentrated in vacuo and 10a 60.102 g, 80%) was obtained
by column chromatography 6hexane±ethyl acetate1:1).
Recrystallisation from ethyl acetate provided an analytically
pure sample of 10a as white needles. Mp: 1808C; 1H NMR
6400 MHz, CDCl3, T315 K, ppm) d 7.3 6m, 5H), 6.11 6dd,
J5.6, 2.9 Hz, 1H), 5.90 6dd, J5.6, 3.1 Hz, 1H), 5.35 6br s,
1H), 4.96 6dd, J14.7, 6.4 Hz, 1H), 4.78 6dd, J14.7,
5.8 Hz, 1H), 3.33 6br s, 1H), 3.23 6d, J4.3 Hz, 1H), 3.20
6br s, 1H), 2.26 6d, J9.1 Hz, 1H), 2.00 6d, J9.1 Hz, 1H);
13C NMR 6100 MHz, CDCl3) d 190.5, 164.8, 137.3, 136.7,
132.3, 129.1, 128.4, 127.5, 105.1, 61.4, 53.6, 50.6, 48.2,
44.4; IR 6KBr, cm21) n 3260, 1674, 1573, 1550, 1494,
1440; HRMS/EI: m/z calcd for C17H15NO35Cl2: 319.05307
6M1). Found: 319.05311 6M1); Anal. calcd for
C17H15NOCl2: C, 63.77; H, 4.72; N, 4.37%. Found: C,
63.79; H, 4.76; N, 4.39%.
4.3.8. 4,6-Dichloro-5-pyrrolidino-endo-tricyclo[5.2.1.02,6]-
deca-4,8-dien-3-one 611b). NCS 60.133 g, 0.99 mmol)
was added to a clear solution of 6e 60.100 g, 0.46 mmol)
in methanol 610 ml). After one day, the reaction mixture was
concentrated in vacuo and dissolved in dichloromethane
610 ml). This mixture was extracted with a 20 ml 0.1 M
NaOH solution. The organicphase was dried over MgSO
4
and concentrated in vacuo. Puri®cation with column chro-
matography 6hexane±ethyl acetate1:1) yielded 11b as a
white solid 60.108 g, 82%). Recrystallisation from ethyl
acetate provided an analytically pure sample of 11b as
1
white needles. Mp: 1438C; H NMR 6400 MHz, CDCl3,
T310 K) d 6.13 6dd, J5.6, 2.9 Hz, 1H), 5.98 6dd,
J5.6, 3.0 Hz, 1H), 4.16±3.76 6m, 4H), 3.32 6br s, 1H),
3.26 6br s, 1H), 3.23 6d, J4.2 Hz, 1H), 2.21 6br d,
J9.1 Hz, 1H), 1.96 6m, 5H); 13C NMR 6100 MHz,
CDCl3, T310 K) d 191.6, 163.0, 137.4, 131.9, 105.2,
74.6, 60.9, 53.9, 50.3, 50.0, 49.8, 45.0, 25.0; IR 6KBr,
cm21) n 1680, 1563, 1456; HRMS/EI: m/z calcd for
C14H15NO635Cl)2: 283.05307 6M1). Found: 283.05318
6M1); Anal. calcd for C14H15NOCl2: C, 59.17; H, 5.32; N,
4.93%. Found: C, 59.45; H, 5.22; N, 5.01%.
4.3.6.
5-Cyclohexylamino-4,6-dichloro-endo-tricyclo-
[5.2.1.02,6]deca-4,8-dien-3-one 610b). NCS 60.294 g,