COMMUNICATIONS
Xian Jiao et al.
by performing the asymmetric oxidation of sulfide and
subsequent kinetic resolution in tandem in the same re-
action vessel. This method is effective only when two im-
portant reaction condition profiles have been predeter-
mined: (i) the time and temperature at which a compro-
mise between sulfoxide yield and ee appears to be rea-
sonable, and (ii) the temperature at which the kinetic
resolution via the unavoidable oxidation of the resulting
enantiomeric sulfoxides is most efficient.
guruma, T. Yamaguchi, J. Minamikawa, S. Otsuka, Tetra-
hedron 2001, 57, 2739±2744; c) M. Matsugi, R. Shimada,
S. Ohata, M. Nojima, N. Fukuda, J. Minamikawa, Y. Kita,
Chem. Pharm. Bull. 2002, 50, 1511±1513.
[
4] a) K. D. Wing, A. H. Glickman, J. E. Casida, Science 19
8
3, 219, 63±65; b) A. H. Glickman, K. D. Wing, J. E. Ca-
sida, Toxicol. Appl. Pharmacol. 1984, 73, 16±22; c) S. Ta-
shiro, H. Miyagawa, N. Sugita, Y. J. Okada, Pestic. Sci.
1
993, 18, 155±164.
[
5] a) G. Solladi e¬ , Synthesis 1981, 185±196, and references
cited therein; b) M. Miko¯aczyk, J. Drabowicz, Top. Ster-
eochem. 1982, 13, 333±394; c) J. D. Barbachyn, C. R.
Johnson, in: Asymmetric Synthesis, (eds.: J. D. Morrison,
J. W. Scott), Academic Press, New York, 1983, Vol. 4,
pp. 227±261; d) G. H. Posner, Acc. Chem. Res. 1987,
20, 72±77; e) K. K. Andersen, in: The Chemistry of Sul-
fones and Sulfoxides, (Eds.: S. Patai, Z. Rappoport,
C. J. M. Stirling), John Wiley & Sons, Ltd., Chichester,
Experimental Section
Typical Procedure for the One-Pot Tandem Catalytic
Oxidation of Sulfides and their Kinetic Resolution
To a solution of (S)-BINOL (57.0 mg, 0.20 mmol) in toluene
(
6 mL) was added dropwise Ti(O-i-Pr) (29.5 mL, 0.10 mmol).
4
1
988, Chapter 3, pp. 55±94; f) G. H. Posner, in: The
After the mixture was stirred for 20 minutes at room tempera-
Chemistry of Sulfones and Sulfoxides, (Eds.: S. Patai, Z.
Rappoport, C. J. M. Stirling), John Wiley & Sons, Ltd.,
Chichester, 1988, Chapter 16, pp. 823±849.
ture, H O(3.6 mL, 0.20 mmol) was added. To the resulting ho-
2
mogeneous solution was added phenyl methyl sulfide (117 mL,
1.0 mmol), and the mixture was stirred at room temperature
for 30 min. The solution was then cooled to 08C, followed by
the addition of TBHP (70% in decane, 0.30 mL, 2 mmol).
The mixture was stirred at 08C for 10 h and then at 258C for an-
other 90 min before being diluted with CH Cl and dried over
[6] a) D. H. Hua, S. N. Bharathi, F. Takusagawa, A. Tsujimo-
to, J. A. K. Panagan, M. H. Hung, A. Bravo, A. M. Er-
plelding, J. Org. Chem. 1989, 54, 5659±5662; b) S. G.
Pyne, P. Bloem, S. L. Chapman, C. E. Dixon, R. Griffth,
J. Org. Chem. 1990, 55, 1086; c) H. B. Kagan, F. Rebiere,
Synlett 1990, 643±650.
2
2
Na SO for a fewmin. After filtration and evaporation of thesol-
2
4
vent, the residue was immediately purified by preparative TLC
Et Oas eluent) or column chromatography (EtOAc). Phenyl
(
2
[7] N. Khair, C. S. Ara u¬ jo, F. Alcudia, I. Fern a¬ ndez, J. Org.
methyl sulfoxide was isolated in 70% yield. The ee value of the
sulfoxide was determined by HPLC on a Daicel Chiralcel OB
column (l¼254 nm; n-hexane:i-PrOH¼80:20; 1.0 mL/min.).
Chem. 2002, 67, 345±356.
[
8] Z. Han, D. Krishnamurthy, P. Grover, H. S. Wilkinson,
Q. K. Fang, X. Su, Z.-H. Lu, D. Magiera, C. H. Sena-
nayake, Angew. Chem. Int. Ed. 2003, 42, 2032±2035.
9] a) F. A. Davis, R. T. Reddy, W. Han, P. J. Caroll, J. Am.
Chem. Soc. 1992, 114, 1428±1437; b) F. A. Davis, H. C.
Weiamiller, J. Am. Chem. Soc. 1989, 111, 5964±5965.
[
Acknowledgements
We thank the University Grants Committee of Hong Kong
[10] J.-M. Brunel, P. Diter, M. Duetsch, H. B. Kagan, J. Org.
Chem. 1995, 60, 8086±8088.
11] H. B. Kagan, in: Catalytic Asymmetric Synthesis, (Ed.: I.
Ojima), Wiley-VCH, New York, 2000, Chapter 6C,
pp. 327±356.
(
Areas of Excellence Scheme, AOE P/10-01) and the Hong
Kong Polytechnic University Area of strategic Development
Fund for the financial support of this study.
[
[
[
12] N. Komatsu, M. Hashizume, T. Sugita, S. Uemura, J. Org.
Chem. 1993, 58, 4529±4533.
13] N. Komatsu, Y. Nishibayashi, T. Sugita, S. Uemura, Tet-
rahedron Lett. 1992, 33, 5391±5394.
References and Notes
≥
University Grants Committee Area of Excellence Scheme
(
Hong Kong).
[14] M. I. Donno, S. Superchi, C. Rosini, J. Org. Chem. 1998,
63, 9392±9395.
[15] S. Superchi, C. Rosini, Tetrahedron: Asymmetry 1997, 8,
349±352.
[1] a) P. Pitchen, Chem. Ind. 1994, 636; b) H. L. Holland,
F. M. Brown, B. G.. Larsen, Tetrahedron: Asymmetry
1
994, 5, 1129±1130; c) C. A. Hutton, J. M. White, Tetra-
hedron Lett. 1997, 38, 1643±1646; d) H. L. Holland,
F. M. Brown, Tetrahedron: Asymmetry 1998, 9, 535±538.
2] a) S. von Unge, V. Langer, L. Sjˆlin, Tetrahedron: Asymme-
try 1997, 8, 1967±1970; b) M. Tanaka, H. Yamazaki; H. Ha-
kasui, N. Nakamichi; H. Sekino, Chirality 1997, 9, 17±21;
c) H. Cotton, T. Elebring, M. Larsson, L. Li, H. Sorensen,
S. Unge, Tetrahedron: Asymmetry 2000, 11, 3819±3825.
3] a) S. Morita, J. Matsubara, K. Otsubo, K. Kitano, T. Oh-
tani, Y. Kawano, M. Uchida, Tetrahedron: Asymmetry
[16] J.-M. Brunel, H. B. Kagan, Synlett. 1996, 404±408.
[17] Y. Yamanoi, T. Imamoto, J. Org. Chem. 1997, 62, 8560±
8564.
[18] a) G.. Lu, X. Li, G. Chen, W. L. Chan, A. S. C. Chan, Tet-
rahedron: Asymmetry 2003, 14, 449±452; b) X. Li, G. Lu,
W. H. Kwok, A. S. C. Chan, J. Am. Chem. Soc. 2002, 124,
12636±12637; c) G. Lu, X. Li, W. L. Chan, A. S. C. Chan,
Chem. Commun. 2002, 172±173.
[
[
[19] H. B. Kagan, J. C. Fiaud, Top. Stereochem. 1988, 18, 249±
330.
1
997, 8, 3707±3710; b) M. Matsugi, N. Fukuda, Y. Mu-
726
¹ 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
Adv. Synth. Catal. 2004, 346, 723±726