Chiral Bioinspired Non-Heme Iron Complexes for Enantioselective Epoxidation of α,β-Unsaturated Ketones

Authors

  • Mei Wu,

    1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Lanzhou 730000, People's Republic of China, Fax: (+86)-931-827-7088; phone: (+86)-931-496-8278
    2. Graduate School of the Chinese Academy of Sciences, Beijing 100039, People's Republic of China
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    • Both authors contributed equally to this work

  • Cheng-Xia Miao,

    1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Lanzhou 730000, People's Republic of China, Fax: (+86)-931-827-7088; phone: (+86)-931-496-8278
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    • Both authors contributed equally to this work

  • Shoufeng Wang,

    1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Lanzhou 730000, People's Republic of China, Fax: (+86)-931-827-7088; phone: (+86)-931-496-8278
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  • Xiaoxue Hu,

    1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Lanzhou 730000, People's Republic of China, Fax: (+86)-931-827-7088; phone: (+86)-931-496-8278
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  • Chungu Xia,

    1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Lanzhou 730000, People's Republic of China, Fax: (+86)-931-827-7088; phone: (+86)-931-496-8278
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  • Fritz E. Kühn,

    1. Molecular Catalysis, Catalysis Research Center, Technische Universität München, 85747 Garching, Germany
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  • Wei Sun

    Corresponding author
    1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Lanzhou 730000, People's Republic of China, Fax: (+86)-931-827-7088; phone: (+86)-931-496-8278
    • State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Lanzhou 730000, People's Republic of China, Fax: (+86)-931-827-7088; phone: (+86)-931-496-8278
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Abstract

Chiral bioinspired iron complexes of N4 ligands based on the ethylenediamine backbone display remarkable levels of enantioselectivity for the first time in the asymmetric epoxidation of α,β-unsaturated ketones using hydrogen peroxide (up to 87% ee) or peracetic acid as oxidant, respectively. Notablely, isotopic labeling with H218O strongly demonstrated that there is a reversible water binding step prior to generation of the significant intermediate. Besides, the complex [L2Fe(III)2(μ-O)(μ-CH3CO2)]3+ usually derived from the decay of the LFe(IV)[DOUBLE BOND]O species or thermodynamic sinks for a number of iron complexes was identified by HR-MS. In addition, the possible mechanisms were proposed and LFe(V)[DOUBLE BOND]O species may be the main active intermediate in the catalytic system.

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