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Switching on elusive organometallic mechanisms with photoredox catalysis

Nature volume 524, pages 330–334 (2015)Cite this article

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Abstract

Transition-metal-catalysed cross-coupling reactions have become one of the most used carbon–carbon and carbon–heteroatom 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, Suzuki–Miyaura, 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 carbon–oxygen 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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Figure 1: Modulating oxidation states of nickel enables challenging carbon–heteroatom coupling.
Figure 2: Proposed mechanism by which photoredox catalysis switches on challenging nickel-catalysed C–O coupling.
Figure 3: Alcohol and aryl halide scope in the photoredox-nickel-catalysed C–O coupling reaction.
Figure 4: Mechanistic studies support the intermediacy of transient Ni(iii) complex to enable C–O reductive elimination.

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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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Authors and Affiliations

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

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

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  1. Jack A. Terrett
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  2. James D. Cuthbertson
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  3. Valerie W. Shurtleff
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  4. 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.

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Correspondence to David W. C. MacMillan.

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The authors declare no competing financial interests.

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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). (PDF 9586 kb)

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Terrett, J., Cuthbertson, J., Shurtleff, V. et al. Switching on elusive organometallic mechanisms with photoredox catalysis. Nature 524, 330–334 (2015). https://doi.org/10.1038/nature14875

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