9763
8. So far only the acidic cyclization of (R)-7a to yield (R)-8 has been reported; see for example: Theisen, P. D.;
Heathcock, C. H. J. Org. Chem. 1993, 58, 142–146.
9. Brown, H. C.; Kim, S. C.; Krishnamurthy, S. J. Org. Chem. 1980, 45, 1–12.
1
10. Selected data for (S)-11: [h]D=+2.3° (c=1, CHCl3); H NMR (C6D6, 300 MHz) 0.17 [s, 6H, Si(CH3)2], 0.93 (s
br, 1H, OH), partially superimposed by 0.94 (d, J=6.5 Hz, 3H, CH3), 1.09 [s, 9H, SiC(CH3)3], 1.26–1.47 (m, 2H,
3-H, 2-HA or 4-HA), 1.55 (dq, J=14.0 Hz, J=7.0 Hz, 1H, 2-HB or 4-HB), 1.65 (dtd, J=14.0 Hz, J=7.0 Hz,
J=6.0 Hz, 1H, 4-HB or 2-HB), 1.84 (mc, 1H, 4-HA or 2-HA), 3.45-3.60 (m br, 2H, 1-H2 or 5-H2), 3.68 (mc, 2H,
5-H2 or 1-H2). The 1H NMR spectrum (500 MHz) of the Mosher ester, prepared from (S)-(−)-a-methoxy-tri-
fluoromethyl-phenylacetic acid and alcohol (S)-11, exhibited only the signals of one diastereoisomer.
11. Negishi, E.; King, A. O.; Klima, W. L. J. Org. Chem. 1980, 45, 2526–2528.
12. For a review see: Negishi, E.; Takahashi, T. Synthesis 1988, 1–19.
13. Selected data for 5: 1H NMR (C6D6, 300 MHz) 1.49 (s, 3H; 6-CH3 or 10-CH3), 1.56 (s, 3H, 14-CH3), 1.60 (s, 3H,
10-CH3 or 6-CH3), 1.66 (s, 3H, 2-CH3), 1.67 (s, 3H, 15-H3), 1.93 (mc, 4H, 3-H2, 4-H2), 2.00–2.22 (m, 8H, 7-H2,
8-H2, 11-H2, 12-H2), 5.04 (mc, 1H, 13-H), 5.22–5.27 (m, 2H, 5-H, 9-H), 5.71 (d, J=0.7 Hz, 1H, 1-H).
14. For a review see: Negishi, E.; Liu, F. In Metal-catalyzed Cross-coupling Reactions; Diederich, F.; Stang, P. J.,
Eds.; Wiley-VCH: Weinheim, 1998, pp. 1–47.
1
15. Selected data for (S)-16: [h]D=−2.6° (c=1, CHCl3); H NMR (C6D6, 200 MHz) 0.90 (d, J=6.0 Hz, 3H, 3-CH3),
1.10–1.51 (m, 5H, 2-H2, 4-H2, OH), 1.55 (mc, 1H, 3-H), 1.66 (s, 3H, 19-CH3), 1.71 (s, 9H, 7-CH3, 11-CH3,
15-CH3), 1.78 (s, 3H, 20-H3), 2.05–2.43 (m, 14H, 5-H2, 8-H2, 9-H2, 12-H2, 13-H2, 16-H2, 17-H2), 3.44–3.70 (m,
2H, 1-H2), 5.21–5.50 (m, 4H, 6-H, 10-H, 14-H, 18-H). The 13C NMR spectrum (125 MHz) of the Mosher ester,
prepared from (S)-(−)-a-methoxy-trifluoromethyl-phenylacetic acid and alcohol (S)-16, exhibited only the signals
of one diastereoisomer.
16. Loupy, A.; Sansoulet, J.; Vaziri-Zand, F. Bull. Soc. Chim. Fr. 1987, 1027–1035.
1
17. Selected data for (S)-1: [h]D=−3.7° (c=1, C6H6); H NMR (C6D6, 200 MHz) 0.89 (d, J=6.5 Hz, 3H, 3%-CH3),
1.12–1.58 (m, 4H, 4%-H2, 2%-H2), 1.61 (s, 3H, 19%-CH3), 1.70–1.80 (m, 1H, 3%-H) superimposed by 1.64–1.71 (3s,
9H, 7%-CH3, 11%-CH3, 15%-CH3) and 1.73 (s, 3H, 20%-H3), 2.02–2.29 (m, 14H, 5%-H2, 8%-H2, 9%-H2, 12%-H2, 13%-H2,
16%-H2, 17%-H2), 3.83 (t, J=6.5 Hz, 2H, 1%-H2), 5.21–5.48 (m, 4H, 6%-H, 10%-H, 14%-H, 18%-H), 7.27–7.47 (m, 3H,
3-H, 7-H, 8-H), 7.56 (d, J=3.0 Hz, 1H, 1-H), 8.15 (d, J=9.6 Hz, 1H, 4-H), 8.34 (dd, J=7.0 Hz, J=2.5 Hz, 2H,
6-H, 9-H).
18. Francis, C. J.; Jones, J. B. J. Chem. Soc., Chem. Commun. 1984, 579–580.
.
.