Titanium-Catalyzed Asymmetric Epoxidation of Olefins with Aqueous Hydrogen Peroxide: Remarkable Effect of Phosphate Buffer on Epoxide Yield

Yuya Shimada; Shoichi Kondo; Yoshio Ohara; Kazuhiro Matsumoto; Tsutomu Katsuki

doi:10.1055/s-2007-985605

LETTER

Titanium-Catalyzed Asymmetric Epoxidation of Olefins with Aqueous Hydrogen Peroxide: Remarkable Effect of Phosphate Buffer on Epoxide Yield

Yuya Shimada^a, Shoichi Kondo^a, Yoshio Ohara^a, Kazuhiro Matsumoto^b, Tsutomu Katsuki*^b
^a Chemical Research Laboratories, Nissan Chemical Industries, Ltd, Tsuboi-chou, Funabashi, Chiba 274-8507, Japan
^b Department of Chemistry, Faculty of Science, Graduate School, Kyushu University, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Fax: +81(92)6422607; e-Mail: katsuscc@mbox.nc.kyushu-u.ac.jp;

Abstract

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Abstract

The practicality of Ti(salan)-catalyzed asymmetric epoxidation was significantly improved by the addition of phosphate buffer (pH 7.4-8.0). Various olefins were transformed on a multigram scale into the corresponding epoxides with nearly complete product selectivity as well as high to excellent enantioselectivity in the presence of 1 mol% of the catalyst and the buffer.

Key words

asymmetric catalysis - epoxidation - titanium - hydrogen peroxide - green chemistry

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References

References and Notes

<A NAME="RU06307ST-1A">1a</A> Jacobsen EN. Wu MH. In Comprehensive Asymmetric Catalysis Vol. 2: Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Heidelberg: 1999. Chap. 21. p.649-677

<A NAME="RU06307ST-1B">1b</A> Katsuki T. In Comprehensive Coordination Chemistry II Vol. 9: McCleverty J. Elsevier Science; Oxford: 2003. Chap. 9.4. p.207-264

<A NAME="RU06307ST-2A">2a</A> Saito B. Katsuki T. Tetrahedron Lett. 2001, 42: 3873

<A NAME="RU06307ST-2B">2b</A> Saito B. Katsuki T. Tetrahedron Lett. 2001, 42: 8333

<A NAME="RU06307ST-2C">2c</A> Tanaka T. Saito B. Katsuki T. Tetrahedron Lett. 2002, 43: 3259

<A NAME="RU06307ST-2D">2d</A> Saito B. Katsuki T. Chirality 2001, 15: 24

<A NAME="RU06307ST-3A">3a</A> Matsumoto K. Sawada Y. Saito B. Sakai K. Katsuki T. Angew. Chem. Int. Ed. 2005, 44: 4935

<A NAME="RU06307ST-3B">3b</A> Sawada Y. Matsumoto K. Katsuki T. Angew. Chem. Int. Ed. 2007, 46: 4559

<A NAME="RU06307ST-4A">4a</A> Juliá S. Masana J. Vega JC. Angew. Chem., Int. Ed. Engl. 1980, 19: 929

<A NAME="RU06307ST-4B">4b</A> Colonna S. Molinari H. Banfi S. Juliá S. Masana J. Alvalez A. Tetrahedron 1983, 39: 1635

<A NAME="RU06307ST-4C">4c</A> Pietikäinen P. Tetrahedron 1994, 50: 941

<A NAME="RU06307ST-4D">4d</A> Irie R. Hosoya N. Katsuki T. Synlett 1994, 255

<A NAME="RU06307ST-4E">4e</A> Berkessel A. Frauenkron M. Schwenkreis T. Steinmetz A. Baum G. Fenske D. J. Mol. Catal. A: Chem. 1996, 113: 321

<A NAME="RU06307ST-4F">4f</A> Pietikäinen P. Tetrahedron 1998, 54: 4319

<A NAME="RU06307ST-4G">4g</A> Arai S. Tsuge H. Shioiri T. Tetrahedron Lett. 1998, 39: 7563

<A NAME="RU06307ST-4H">4h</A> Francis MB. Jacobsen EN. Angew. Chem. Int. Ed. 1999, 38: 937

<A NAME="RU06307ST-4I">4i</A> Shu L. Shi Y. Tetrahedron 2001, 57: 5213

<A NAME="RU06307ST-4J">4j</A> Kureshy RI. Khan NH. Abdi SHR. Singh S. Ahmed I. Shunkla RS. Jasra RV. J. Catal. 2003, 219: 1

<A NAME="RU06307ST-4K">4k</A> Tse MK. Döbler C. Bhor S. Klawonn M. Mägerlein W. Hugl H. Beller M. Angew. Chem. Int. Ed. 2004, 43: 5255

<A NAME="RU06307ST-4L">4l</A> Marigo M. Franzén J. Poulsen TB. Zhuang W. Jørgensen KA. J. Am. Chem. Soc. 2005, 127: 6964

<A NAME="RU06307ST-4M">4m</A> Colladon M. Scarso A. Sgarbossa P. Michelin RA. Strukul G. J. Am. Chem. Soc. 2006, 128: 14006

<A NAME="RU06307ST-4N">4n</A> Tse MK. Bhor S. Klawonn M. Anilkumar G. Jiao H. Spannenberg A. Döbler C. Mägerlein W. Hugl H. Beller M. Chem. Eur. J. 2006, 12: 1875

<A NAME="RU06307ST-4O">4o</A> Colladon M. Scarso A. Sgarbossa P. Michelin RA. Strukul G. J. Am. Chem. Soc. 2007, 129: 7680

<A NAME="RU06307ST-5">5</A> Sawada Y. Matsumoto K. Kondo S. Watanabe H. Ozawa T. Suzuki K. Saito B. Katsuki T. Angew. Chem. Int. Ed. 2006, 45: 3478

<A NAME="RU06307ST-6">6</A> Matsumoto K. Sawada Y. Katsuki T. Synlett 2006, 3545

The main byproducts are hydroperoxyalcohols and diols.

A phospate buffer of pH 7.4-8.0 can be used for the purpose of suppressing the decomposition of epoxides.

Other buffers such as acetate, citrate, and borate buffers were also effective.

<A NAME="RU06307ST-10A">10a</A> Lane BS. Vogt M. DeRose VJ. Burgess K. J. Am. Chem. Soc. 2002, 124: 11946

<A NAME="RU06307ST-10B">10b</A> Grigoropoulou G. Clark JH. Tetrahedron Lett. 2006, 47: 4461

Unfortunately, reactions of aliphatic olefins were low productive in view of both yield and enantioselectivity, even under the optimized conditions.

In a large-scale synthesis, the addition of an excess amount of ligand was not required, while the excess ligand was added in a small scale in order to obtain reproducibility.