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Enantioselective Synthesis of Epoxides Having a Tetrasubstituted Trifluoromethylated Carbon Center: Methylhydrazine-Induced Aerobic Epoxidation of β,β-Disubstituted Enones

Authors

  • Hiroyuki Kawai,

    1. Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
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  • Satoshi Okusu,

    1. Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
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  • Zhe Yuan,

    1. Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
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  • Etsuko Tokunaga,

    1. Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
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  • Akihito Yamano,

    1. Rigaku Corporation, 3-9-12 Mastubara-cho, Akishima Tokyo 196-8666 (Japan)
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  • Dr. Motoo Shiro,

    1. Rigaku Corporation, 3-9-12 Mastubara-cho, Akishima Tokyo 196-8666 (Japan)
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  • Prof. Norio Shibata

    Corresponding author
    1. Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
    • Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)===

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  • This study was financially supported in part by Grants-in-Aid for Scientific Research from the MEXT (Ministry of Education, Culture, Sports, Science and Technology) (24105513, Project No. 2304: Advanced Molecular Transformation by Organocatalysts). We thank the Asahi Glass Foundation for partial support. E.T. acknowledges Grants-in-Aid for Scientific Research for financial support (24915016). We also thank INSA de Rouen, France for providing an internship for Z.Y.

Abstract

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The unprecedented title reaction is catalyzed by a methylhydrazine/base/organocatalyst (1) system. Biologically attractive epoxides (2) having a tetrasubstituted trifluoromethylated carbon center were obtained with excellent enantioselectivity for the first time. 18O-labeling experiments suggest a mechanism involving the activation of molecular oxygen. MTBE=methyl tert-butyl ether.

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