T. Mino et al. / Journal of Organometallic Chemistry 691 (2006) 4297–4303
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3.4. Preparation of (1R,4R)-7,7-dimethyl-1-
(hydroxydiphenylmethyl)-bicyclo[2,2,1]heptan-2- one (8)
[10]
2.70–2.80 (m 5H), 3.52–3.75 (m 4H), 6.02 (br 1H), 7.13–
7.52 (m 10H); 13C-NMR (CDCl3) d: 21.5, 22.4, 27.0,
28.0, 35.1, 46.1, 50.6, 55.4, 63.0, 66.4, 81.0, 126.5, 127.0,
127.3, 129.2, 130.4, 145.6, 148.9, 179.4, 182.8; IR (film):
3392 and 1639 cmꢀ1; FAB-MS m/z (rel. intensity): 405
(M+ + 1, 38); HR-MS Calc. for C26H33N2O (M+ + H)
405.2542. Found 405.2558.
To solution of ketoester 7 (0.99 g, 5.0 mmol) in THF
(20 mL) was added phenyl lithium (11.0 mmol) in THF
(1.1 M, 9.6 mL) at ꢀ78 °C under an argon atmosphere.
After being stirred for 18 h, the reaction mixture was
diluted with ether and water. The organic layer was washed
with brine and dried over MgSO4. The filtrate was concen-
trated with a rotary evaporator and the residue was puri-
3.5.3. (1R,4R)-7,7-Dimethyl-1-(hydroxydiphenylmethyl)-
bicyclo[2,2,1]heptan-2-one SAMP hydrazone (3c)
61%; ½aꢁD ¼ þ288 (c = 0.3, CHCl3); 1H-NMR
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fied by column chromatography: 64%; ½aꢁD ¼ þ183
(CDCl3) d: 0.12 (s, 3H), 1.09 (s, 3H), 1.24–1.29 (m, 1H),
1.55–1.58 (m, 2H), 1.82–1.89 (m, 5H), 2.46–2.59 (m, 4H),
3.00–3.10 (m, 1H), 3.29–3.33 (m, 6H), 6.30 (br, 1H),
7.26–7.28 (m, 3H), 7.45–4.45 (m, 4H), 7.48–7.49 (m, 3H);
13C-NMR (CDCl3) d: 21.6, 22.3, 22.7, 26.3, 27.0, 28.4,
35,9, 46.3, 50.6, 54.9, 59.4, 62.6, 66.1, 76.2, 80.9, 126.1,
126.8, 126.8, 127.2, 128.9, 130.4, 145.9, 149.6, 171.9; IR
(film): 3389 and 1658 cmꢀ1; FAB-MS m/z (rel. intensity):
433 (M+ + 1, 75); HR-MS Calc. for C28H37N2O
(M+ + H) 433.2855. Found 433.2859.
1
(c = 0.3, CHCl3); m.p. 186–187 °C; H-NMR (CDCl3) d:
0.26 (s, 3H), 1.07 (s, 3H), 1.39–1.45 (m, 1H), 1.78 (t,
J = 4.8 Hz, 1H), 1.90–1.99 (m, 2H), 2.05–2.32 (m, 1H),
2.48–2.54 (m, 2H), 3.83 (br, 1H), 7.17–7.47 (m, 10H);
13C-NMR (CDCl3) d: 21.6, 22.6, 25.5, 26.9, 43.5, 44.5,
50.2, 69.2, 79.8, 126.8, 126.9, 127.1, 127.3, 128.2, 129.1,
144.5, 147.1, 220.2; IR (film): 3498 and 1714 cmꢀ1; EI-
MS m/z (rel. intensity): 320 (M+, 8); HR-MS Calc. for
C22H24O2 (M+) 320.1776. Found 320.1768.
3.5. Typical procedure for the preparation of 3 and 4
3.5.4. (1R,4R)-7,7-Dimethyl-1-(hydroxydiphenylmethyl)-
bicyclo[2,2,1]heptan-2-one RAMP hydrazone (3d)
64%; ½aꢁD ¼ þ165 (c = 0.3, CHCl3); 1H-NMR
20
To solution of hydrazine or amine (0.5 mmol) in toluene
(1 mL) was added trimethylaluminium (0.5 mmol) in hex-
ane (1.0 M, 0.5 mL) under an argon atmosphere. The mix-
ture was heated under reflux for 3 h, and then the solution
of ketoalcohol 8 (0.080 g, 0.25 mmol) in toluene (1 mL)
was added. After the mixture was heated under reflux for
4 h, the reaction mixture was diluted with ether and water.
The organic layer was washed with brine and dried over
MgSO4. The filtrate was concentrated with a rotary evapo-
rator and the residue was purified by column
chromatography.
(CDCl3) d: 0.09 (s, 3H), 1.11 (s, 3H), 1.21–1.27 (m, 2H),
1.52–1.58 (m, 1H), 1.73–1.79 (m, 4H), 2.03 (d,
J = 17.5 Hz, 1H), 2.23–2.51 (m, 2H), 2.53–2.79 (m, 2H),
2.98–3.23 (m, 4H), 3.25 (s, 3H), 5.83 (br, 1H), 7.11–7.48
(m, 10H); 13C-NMR (CDCl3) d: 21.5, 22.6, 22.7, 26.4,
27.8, 27.9, 36.3, 46.5, 50.7, 54.3, 59.5, 63.3, 66.9, 74.9,
80.8, 126.3, 126.9, 127.1, 127.3, 129.1, 130.2, 145.8, 149.5,
173.8; IR (film): 3368 and 1637 cmꢀ1; FAB-MS m/z (rel.
intensity): 433 (M+ + 1, 78); HR-MS Calc. for
C28H37N2O2 (M+ + H) 433.2855. Found 433.2849.
3.5.1. (1R,4R)-7,7-Dimethyl-1-(hydroxydiphenylmethyl)-
bicyclo[2,2,1]heptan-2-one DMH hydrazone (3a)
3.5.5. (1R,4R)-7,7-Dimethyl-1-(hydroxydiphenylmethyl)-
bicyclo[2,2,1]heptan-2-ylidene)-(S)-1-phenylethanamine
(4a)
51%; ½aꢁD ¼ þ275 (c = 0.31, CHCl3); 1H-NMR
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(CDCl3) d: 0.07 (s, 3H), 1.08 (s, 3H), 1.25–1.34 (m, 1H),
1.57 (t, J = 4.5 Hz, 1H), 1.76–1.81 (m, 1H), 2.01 (dd,
J = 4.5 Hz and 17.7 Hz, 1H), 2.27–2.48 (m, 2H), 2.47 (s,
6H), 2.69–2.78 (m, 1H), 6.18 (br, 1H), 7.14–7.26 (m, 6H),
7.36–7.52 (m, 4H); 13C-NMR (CDCl3) d: 21.1, 21.8, 26.6,
27.6, 34.5, 45.7, 47.3, 50.2, 62.4, 80.7, 126.0, 126.5, 126.6,
126.9, 127.2, 127.3, 128.8, 129.1, 130.2, 145.3, 148.6,
177.9; IR (film): 3365 and 1651 cmꢀ1; FAB-MS m/z (rel.
intensity): 363 (M+ + 1, 70); HR-MS Calc. for
C24H31N2O (M+ + H) 363.2436. Found 363.2441.
40%; ½aꢁD ¼ þ123 (c = 1.0, CHCl3); m.p. 77–78 °C;
1H-NMR (CDCl3) d: 0.07 (s, 3H), 1.14 (s, 3H), 1.20–1.25
(m, 1H), 1.37 (d, J = 16.5 Hz, 3H), 1.55–1.62 (m, 1H),
1.68–1.80 (m, 1H), 1.87 (d, J = 17.0 Hz, 1H), 2.18–2.29
(m, 1H), 2.41–2.43 (m, 1H), 2.61–2.62 (m, 1H), 4.55 (q,
J = 6.5 Hz, 1H), 6.13 (br, 1H), 7.07–7.69 (m, 15H); 13C-
NMR (CDCl3) d: 21.0, 21.8, 24.8, 26.8, 27.4, 34.4, 45.7,
49.6, 60.7, 63.4, 65.8, 80.7, 126.0, 126.3, 126.4, 126.5,
126.7, 126.8, 128.4, 128.7, 130.1, 144.8, 145.2, 148.7,
180.8; IR (film): 2964 and 1670 cmꢀ1; EI-MS m/z (rel.
intensity): 423 (M+, 10); HR-MS Calc. for C30H34NO
(M+ + H) 424.2640. Found 424.2627.
3.5.2. (1R,4R)-7,7-Dimethyl-1-(hydroxydiphenylmethyl)-
bicyclo[2,2,1]heptan-2- one 1-aminomorpholine hydrazone
(3b)
3.5.6. (1R,4R)-7,7-Dimethyl-1-(hydroxydiphenylmethyl)-
bicyclo[2,2,1]heptan-2- ylidene)(phenyl)methanamine (4b)
20
62%; ½aꢁD ¼ þ221 (c = 1.0, CHCl3); m.p. 149–152 °C;
1H-NMR (CDCl3) d: 0.08 (s 3H), 1.08 (s 3H), 1.28–1.32
(m, 1H), 1.57–1.61 (m 1H), 1.75–1.84 (m 1H), 1.95 (d,
J = 17.9 Hz, 1H), 2.26–2.44 (m, 1H), 2.48–2.50 (m 1H),
53%; ½aꢁD ¼ þ277 (c=1.0, CHCl3); H-NMR (CDCl3)
d: 0.08 (s, 3H), 1.06 (s, 3H), 1.17–1.29 (m, 1H), 1.60–1.63
(m, 1H), 1.76–1.80 (m, 1H), 1.92 (d, J = 17.2 Hz, 1H),
1
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