S. Nakamura et al. / Tetrahedron 57 (2001) 8469±8480
8479
Â
C.; Rodriguez, J. H.; Rubio, A.; Sanchez, J.; Solladie, G.
J. Org. Chem. 1990, 55, 2120. )e) Barros, D.; CarrenÄo,
M. C.; Ruano, J. L. G.; Maestro, M. C. Tetrahedron Lett.
1992, 33, 2733. )f) Bueno, A. B.; CarrenÄo, M. C.; Ruano,
J. L. G.; Pena, B.; Rubio, A.; Hoyos, M. A. Tetrahedron
1994, 50, 9355. For reduction of b-ketosulfoxides with other
reducing reagents: see, )g) Annunziata, R.; Cinquini, M.;
Cozzi, F. J. Chem. Soc., Perkin Trans. 1 1979, 1687.
)COSMOSIL hexane/ethyl acetate75:25, ¯ow rate
p
p
0.50 mL min21) tR 23.5 )SS ,Rp) and 27.0 )SS ,Sp) min.
5.6.8. ꢀSS ,Sp)- and ꢀSS ,Rp)-3-Hydroxy-1-phenyl-3-[2-
p
p
[ꢀ2,4,6-triisopropylphenyl)sul®nyl]phenyl]-1-propanones
p
p
[ꢀSS ,Sp)-15 and ꢀSS ,Rp)-15]. To a solution of 1c )38.6 mg,
0.108 mmol) in CH2Cl2 )0.5 mL) was added BF3´OEt2
)1.34 mol L21 solution in CH2Cl2, 0.16 mL, 0.214 mmol)
at 2788C and the mixture was stirred for 1 h. A solution
of O-trimethylsilyl enol ether of acetophenone )32.0 mg,
0.166 mmol) in CH2Cl2 )0.5 mL) was then added. After
stirring for 3 h, HCl )1 mol L21) was added and the mixture
was stirred for 15 min. Usual workupgave the crude product
which was puri®ed by column chromatography )silica gel
Â
)h) Solladie, G.; Greck, C.; Demailly, G. Tetrahedron Lett.
1982, 23, 5047. )i) Ogura, K.; Fujita, M.; Inaba, T.; Takahashi,
K.; Iida, H. Tetrahedron Lett. 1983, 24, 503. )j) Guanti, G.;
Narisano, E.; Pero, F.; Ban®, L.; Scolastico, C. J. Chem. Soc.,
Perkin Trans. 1 1984, 189. )k) Paule, S. D. D.; Piombo, L.;
Ã
Ratovelomanana-Vidal, V.; Greck, C.; Genet, J.; Eur J. Org.
Chem. 2000, 1535.
p
10 g, hexane/ethyl acetate85:15) to afford )SS ,Sp)-15
p
)28.4 mg, 55%) and )SS ,Rp)-15 )14.9 mg, 29%). The dia-
2. For nucleophilic reactions of b-ketosulfoxides: see, )a)
Kunieda, N.; Nokami, J.; Kinoshita, M. Chem. Lett. 1974,
369. )b) Annunziata, R.; Cinquini, M.; Cozzi, F. J. Chem.
stereomer ratio was determined to be 58:42 by the 1H NMR
analysis of the crude product. )SS ,Sp)-15; Rf0.20 )hexane/
p
1
Â
Soc., Perkin Trans. 1 1979, 1687. )c) Solladie, G.; Greck,
Â
C.; Demailly, G.; Solladie-Cavallo, A. Tetrahedron Lett.
ethyl acetate80:20); H NMR d 1.05 )d, 6H, J6.9 Hz),
1.16 )d, 6H, J6.9 Hz), 1.27 )d, 6H, J6.9 Hz), 2.90 )hep,
1H, J6.9 Hz), 3.32 )dd, 1H, J9.0, 17.3 Hz), 3.67 )hep,
2H, J6.9 Hz), 3.84 )dd, 1H, J3.4, 17.3 Hz), 4.29 )d, 1H,
J4.3 Hz), 5.72 )ddd, 1H, J3.4, 4.3, 9.0 Hz), 7.13 )s, 2H),
7.30±7.80 )m, 7H), 7.95±8.05 )m, 2H); 13C NMR d 23.7,
24.2, 29.2, 34.4, 46.6, 68.0, 123.4, 125.9, 127.8, 128.4,
128.6, 130.7, 133.6, 141.8, 143.0, 151.1, 153.5; IR )neat)
3400, 2980, 1680, 1260, 1060 cm21; EIMS m/z )rel. inten-
sity) 476 )M1, 0.2), 290 )100), 256 )95), 105 )98); Anal.
Calcd for C30H36O3S: C,75.59; H, 7.61. Found: C, 75.44; H,
1982, 23, 5047. )d) Ogura, K.; Fujita, M.; Inaba, T.;
Takahashi, K.; Iida, H. Tetrahedron Lett. 1983, 24, 503.
)e) Guanti, G.; Narisano, E.; Pero, F.; Ban®, L.; Scolastico,
C. J. Chem. Soc., Perkin Trans. 1 1984, 189. )f) Fujisawa, T.;
Fujimura, A.; Ukaji, Y. Chem. Lett. 1988, 1541. )g) Bueno,
A. B.; Carreno, M. C.; Fischer, J.; Ruano, J. L. G.; Pena, B.;
Ä
Penas, L.; Rubio, A. Tetrahedron Lett. 1991, 32, 3191.
Ä
Ä
3. For reduction of g-ketosulfoxides: see, )a) Arai, Y.; Suzuki,
A.; Masuda, T.; Masaki, Y.; Shiro, M. Chem. Pharm. Bull.
7.73. )SS ,Rp)-15: Rf0.11 )hexane/ethyl acetate80:20);
Â
1996, 44, 1756. )b) Solladie, G.; Hanquet, G.; Rolland, C.
Â
Tetrahedron Lett. 1997, 38, 5847. )c) Solladie, G.; Colobert,
Â
F.; Somny, F. Tetrahedron Lett. 1999, 40, 1227. )d) Solladie,
p
1H NMR d 0.83 )d, 6H, J6.9 Hz), 0.94 )d, 6H,
J6.9 Hz), 1.25 )d, 6H, J6.9 Hz), 2.15 )dd, 1H, J3.0,
18.0 Hz), 2.43 )hep, 1H, J6.9 Hz), 3.05 )dd, 1H, J9.3,
18.0 Hz), 3.80 )hep, 2H, J6.9 Hz), 4.15 )d, 1H, J3.0 Hz),
5.37 )ddd, 1H, J3.0, 3.0, 9.3 Hz), 6.92 )s, 2H), 7.35±7.85
)m, 9H); 13C NMR d 23.0, 23.4, 24.6, 29.1, 33.8, 449., 65.7,
123.2, 125.7, 127.2, 128.1, 128.6, 130.4, 133.5, 135.1,
136.3, 140.7, 141.9, 151.2, 153.7; IR )neat) 3450, 2980,
1680, 1630, 1060, 1030, 890 cm21; EIMS m/z )rel. inten-
sity) 476 )M1, 0.2), 290 )100), 283 )90), 256 )95); Anal.
Calcd for C30H36O3S: C,75.59; H, 7.61. Found: C, 75.43; H,
7.89.
G.; Hanquet, G.; Izzo, I.; Crumbie, R. Tetrahedron Lett. 1999,
40, 3071. For nucleophilic additions to g-ketosulfoxide: see,
)e) Girodier, L. D.; Rouessac, F. P. Tetrahedron: Asymmetry
1994, 5, 1203. )f) Arai, Y.; Masuda, T.; Masaki, Y.; Koizumi,
T. Heterocycles 1994, 38, 1751. )g) Arai, Y.; Suzuki, A.;
Masuda, T.; Masaki, Y.; Shiro, M. J. Chem. Soc., Perkin
Trans. 1 1995, 2913. )h) Arai, Y.; Masuda, T.; Masaki, Y.
Synlett 1997, 1459.
4. Nakamura, S.; Kuroyanagi, M.; Watanabe, Y.; Toru, T.
J. Chem. Soc., Perkin Trans. 1 2000, 3143.
5. )a) Nakamura, S.; Yasuda, H.; Watanabe, Y.; Toru, T.
Tetrahedron Lett. 2000, 41, 4157. )b) Nakamura, S.; Yasuda,
H.; Watanabe, Y.; Toru, T. J. Org. Chem. 2000, 65, 8640.
6. Huet, F.; Lechevallier, A.; Pellet, M.; Conia, J. M. Synthesis
1978, 63.
Acknowledgements
We thank Dr Shinya Kusuda, Ono Pharmaceutical Co., Ltd,
for the X-ray crystallographic analyses. This work was
partly supported by a Grant-in-Aid for Scienti®c Research
)no. 13450369) from the Ministry of Education, Science,
Sports and Culture of Japan and the Sasakawa Scienti®c
Research Grant from The Japan Science Society.
7. )a) Harms, A. F.; Hespe, W.; Nauta, W. T.; Rekker, R. F.;
È
Timmerman, H.; de Vries, J. In Drug Design; Ariplens, E. J.,
Ed.; Acsdemic: New York, 1976; Vol. 6, pp. 1±80.
)b) Stanchev, S.; Rakovska, R.; Berova, N.; Snatzke, G.
Tetrahedron: Asymmetry 1995, 6, 183. )c) Botta, M.;
Summa, V.; Corelli, F.; Pietro, G. D.; Lombardi, P. Tetrahe-
dron: Asymmetry 1996, 7, 1263.
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