Transition-Metal-Catalyzed Alkylations of Amines with Alkyl Halides: Photoinduced, Copper-Catalyzed Couplings of Carbazoles

Authors

  • Dr. Alex C. Bissember,

    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (USA)
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  • Dr. Rylan J. Lundgren,

    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (USA)
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    • These authors contributed equally to this work.

  • Sidney E. Creutz,

    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (USA)
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    • These authors contributed equally to this work.

  • Prof. Jonas C. Peters,

    Corresponding author
    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (USA)
    • Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (USA)

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  • Prof. Gregory C. Fu

    Corresponding author
    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (USA)
    • Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (USA)

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  • This work was supported by the Gordon and Betty Moore Foundation (grant to J.C.P.), the National Science Foundation (fellowship support for S.E.C.), and the Natural Sciences and Engineering Research Council of Canada (fellowship support for R.J.L.). Assistance with X-ray crystallography from Larry M. Henling is gratefully acknowledged.

Abstract

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N-alkylations of carbazoles with a variety of secondary and hindered primary alkyl iodides can be achieved by using a simple precatalyst (CuI) under mild conditions (0 °C) in the presence of a Brønsted base; at higher temperature (30 °C), secondary alkyl bromides also serve as suitable coupling partners. A Li[Cu(carbazolide)2] complex has been crystallographically characterized, and it may serve as an intermediate in the catalytic cycle.

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