Copper-Catalyzed 1,4-Addition of Organoboronates to Alkylidene Cyanoacetates: Mechanistic Insight and Application to Asymmetric Catalysis

Authors

  • Keishi Takatsu,

    1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988
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  • Dr. Ryo Shintani,

    Corresponding author
    1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988
    • Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988
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  • Prof. Dr. Tamio Hayashi

    Corresponding author
    1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988
    • Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988
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  • Support has been provided in part by a Grant-in-Aid for Young Scientists (B), the Ministry of Education, Culture, Sports, Science, and Technology (Japan), and in part by Mitsubishi Tanabe Pharma Corporation. K.T. thanks the JSPS for a fellowship.

Abstract

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In addition: A copper/N-heterocyclic carbene(NHC)-catalyzed 1,4-addition of organoboronates to alkylidene cyanoacetates was developed, in which the catalytic cycle is proposed to consist of a transmetalation/insertion/ligand exchange. An effective asymmetric variant has also been achieved by the use of a chiral NHC ligand (see scheme).

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