Letter | Published:

Switching on elusive organometallic mechanisms with photoredox catalysis

Nature volume 524, pages 330334 (20 August 2015) | Download Citation

Abstract

Transition-metal-catalysed cross-coupling reactions have become one of the most used carboncarbon and carbonheteroatom bond-forming reactions in chemical synthesis. Recently, nickel catalysis has been shown to participate in a wide variety of C−C bond-forming reactions, most notably Negishi, SuzukiMiyaura, Stille, Kumada and Hiyama couplings1,2. Despite the tremendous advances in C−C fragment couplings, the ability to forge C−O bonds in a general fashion via nickel catalysis has been largely unsuccessful. The challenge for nickel-mediated alcohol couplings has been the mechanistic requirement for the critical C–O bond-forming step (formally known as the reductive elimination step) to occur via a Ni(iii) alkoxide intermediate. Here we demonstrate that visible-light-excited photoredox catalysts can modulate the preferred oxidation states of nickel alkoxides in an operative catalytic cycle, thereby providing transient access to Ni(iii) species that readily participate in reductive elimination. Using this synergistic merger of photoredox and nickel catalysis, we have developed a highly efficient and general carbonoxygen coupling reaction using abundant alcohols and aryl bromides. More notably, we have developed a general strategy to ‘switch on’ important yet elusive organometallic mechanisms via oxidation state modulations using only weak light and single-electron-transfer catalysts.

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Acknowledgements

Financial support was provided by the National Institute of General Medical Sciences (R01 GM093213-01) and gifts from Merck, AbbVie and Bristol-Myers Squibb. J.A.T. thanks Bristol-Myers Squibb for a Graduate Fellowship. J.D.C. thanks Marie Curie Actions for an International Outgoing Fellowship. The authors thank Eric R. Welin for assistance in preparing Ni(ii) complexes.

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  1. Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, USA

    • Jack A. Terrett
    • , James D. Cuthbertson
    • , Valerie W. Shurtleff
    •  & David W. C. MacMillan

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Contributions

J.A.T., J.D.C. and V.W.S. performed and analysed experiments. J.A.T., J.D.C., V.W.S. and D.W.C.M. designed experiments to develop this reaction and probe its utility, and also prepared this manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to David W. C. MacMillan.

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    Supplementary Information

    This file contains Supplementary Text and Data, Supplementary Figures 1–11, NMR spectral data for novel compounds and additional references (see Contents for details).

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DOI

https://doi.org/10.1038/nature14875

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