R. Baati et al. / Tetrahedron Letters 43 (2002) 959–961
961
Acknowledgements
12. (a) Prepared (86–96% yield) from commercial bromide (1
mmol), CHCl3 (2 mmol), and NaH (2 mmol) in DMF (15
mL) at 0°C for 6 h. See, Rachid Baati, Ph.D. Thesis,
Universite´ Louis Pasteur de Strasbourg, 2000; (b) from 9
(95%) via Pd/C/H2 in EtOH; (c) from 9 via a-AD-mix
(CH2Cl2, 4°C; 89%), then Me2C(OMe)2/PTSA (CH2Cl2,
23°C; 95%); (d) from 9 via a-AD-mix (CH2Cl2, 4°C;
89%), then Ac2O/py (CH2Cl2, 23°C; 92%); (e) according
to Morimoto, T.; Sekiya, M. Synthesis 1981, 308–310
using trichloroethanol and benzyl bromide (85%) or 2-
bromo-4%-methoxybenzophenone (82%); (f) from 19 via
olefination with Ph3PCHCO2Me (C6H6, 100°C; 85%) or
Ph3PCH3Br (BuLi, −78°C to rt, THF; 80%).
Financial support provided by the Robert A. Welch
Foundation, NIH (GM31278, DK38226), CNRS, Insti-
tuts de Recherches Pierre Fabre (to R.B.), and an
unrestricted grant from Taisho Pharmaceutical Co.,
Ltd. Dr. E. R. Fogel is warmly thanked for insightful
discussions.
References
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13. Spectral data for 3: H NMR (CDCl3, 300 MHz) l 4.01
(s, 2H), 6.39–6.42 (m, 1H), 6.45–6.48 (m, 1H), 7.43–7.46
(m, 1H); 13C NMR (CDCl3, 75 MHz) l 53.21, 97.35,
1
110.90, 111.37, 143.13, 147.87. 9: H NMR (CDCl3, 300
MHz) l 4.22 (s, 2H), 7.40–7.60 (m, 2H), 7.80–7.86 (m,
2H); 13C NMR (CDCl3, 75 MHz) l 57.97, 98.71, 16.98,
1
127.37, 130.20, 133.24, 133.65. 10: H NMR (CDCl3, 300
MHz) l 6.41 (d, 1H, J=6.0 Hz), 6.86 (d, 1H, J=6.0 Hz),
7.14–7.22 (m, 1H), 7.30–7.36 (m, 1H), 7.56–7.66 (m, 1H),
7.83 (d, 1H, J=5.7 Hz); 13C NMR (CDCl3, 75 MHz) l
120.09, 124.17, 127.16, 129.14, 129.71, 130.91, 132.87,
1
134.12. 12: H NMR (CDCl3, 300 MHz) l 2.50–2.60 (m,
2H), 2.73 (t, 2H, J=7.2 Hz), 5.77 (dd, 1H, J=7.2, 14.1
Hz), 6.04 (d, 1H, J=6.9 Hz), 7.20–7.38 (m, 5H); 13C
NMR (CDCl3, 75 MHz) l 28.87, 34.66, 117.37, 118.85,
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1
126.26, 128.63, 130.95, 141.45. 15: H NMR (CDCl3, 300
MHz) l 2.02 (s, 3H), 2.12 (s, 3H), 2.89 (dd, 1H, J=1.80,
15.30 Hz), 2.99 (dd, 1H, J=7.5, 15.3 Hz), 5.78–5.90 (m,
2H), 7.30–7.42 (m, 5H); 13C NMR (CDCl3, 75 MHz) l
21.09, 21.12, 54.71, 71.03, 75.74, 96.66, 127.44, 128.90,
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1
129.18, 135.66, 169.46, 169.74. 16: H NMR (CDCl3, 300
MHz) l 2.03 (s, 3H), 2.10 (s, 3H), 5.60–5.70 (m, 1H), 5.94
(d, 1H, J=9.0 Hz), 6.06–6.17 (m, 2H), 7.20–7.40 (m, 5H).
1
19: H NMR (CDCl3, 300 MHz) l 3.88 (s, 3H), 4.30 (s,
2H), 5.08 (s, 2H), 6.96 (d, 2H, J=9.0 Mz), 7.92 (d, 2H,
J=9.0 Hz). 20: 1H NMR (CDCl3, 300 MHz) l 3.88 (s,
3H), 5.08 (s, 2H), 5.24 (d, 1H, J=4.2 Hz), 6.38 (d, 1H,
J=4.2 Hz), 6.96 (d, 2H, J=9.0 Mz), 7.92 (d, 2H, J=9.0
Hz).
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16. Alternatively, CrCl2 can be prepared from less expensive
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