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Iron-Catalyzed C[BOND]H Bond Activation for the ortho-Arylation of Aryl Pyridines and Imines with Grignard Reagents

Authors

  • Dr. Naohiko Yoshikai,

    1. Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan), Fax: (+81) 3-5800-6889
    2. Present address: Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)
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  • Sobi Asako,

    1. Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan), Fax: (+81) 3-5800-6889
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  • Takeshi Yamakawa,

    1. Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan), Fax: (+81) 3-5800-6889
    2. Present address: Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)
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  • Dr. Laurean Ilies,

    1. Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan), Fax: (+81) 3-5800-6889
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  • Prof. Dr. Eiichi Nakamura

    Corresponding author
    1. Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan), Fax: (+81) 3-5800-6889
    • Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan), Fax: (+81) 3-5800-6889

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Abstract

Direct arylation of the ortho-C[BOND]H bond of an aryl pyridine or an aryl imine with an aryl Grignard reagent has been achieved by using an iron-diamine catalyst and a dichloroalkane as an oxidant in a short reaction time (e.g., 5 min) under mild conditions (0 °C). The use of an aromatic co-solvent, such as chlorobenzene and benzene, and slow addition of the Grignard reagent are essential for the high efficiency of the reaction. The present arylation reaction has distinct merits over the previously developed reaction that used an arylzinc reagent, such as its reaction rate and atom economy. Selective C[BOND]H bond activation occurs in the presence of a leaving group, such as a tosyloxy, chloro, and bromo group. Studies on a stoichiometric reaction and kinetic isotope effects shed light on the reaction intermediate and the C[BOND]H bond-activation step.

Abstract

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