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The merger of transition metal and photocatalysis

Abstract

The merger of transition metal catalysis and photocatalysis, termed metallaphotocatalysis, has recently emerged as a versatile platform for the development of new, highly enabling synthetic methodologies. Photoredox catalysis provides access to reactive radical species under mild conditions from abundant, native functional groups, and, when combined with transition metal catalysis, this feature allows direct coupling of non-traditional nucleophile partners. In addition, photocatalysis can aid fundamental organometallic steps through modulation of the oxidation state of transition metal complexes or through energy-transfer-mediated excitation of intermediate catalytic species. Metallaphotocatalysis provides access to distinct activation modes, which are complementary to those traditionally used in the field of transition metal catalysis, thereby enabling reaction development through entirely new mechanistic paradigms. This Review discusses key advances in the field of metallaphotocatalysis over the past decade and demonstrates how the unique mechanistic features permit challenging, or previously elusive, transformations to be accomplished.

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Figure 1: Key features of transition metal and photoredox catalysis that provide access to elusive reactivity.
Figure 2: Dual photoredox nickel-catalysed C–C bond formation through oxidative radical generation.
Figure 3: C–H arylation by dual nickel photoredox catalysis.
Figure 4: Cross-electrophile coupling mediated by a silyl radical.
Figure 5: Visible light-enabled Ni-catalysed C–X bond-forming reactions.
Figure 6: Light-enabled C–H functionalization using dual palladium photoredox catalysis.
Figure 7: Visible light-enabled decarboxylative coupling using metallaphotoredox catalysis.
Figure 8: Formation of C–C and C–N bonds using dual copper photoredox catalysis.
Figure 9: Oxyarylation and aminoarylation of alkenes through dual gold photoredox catalysis.
Figure 10: Arylative functionalization mediated by dual gold photoredox catalysis.

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Acknowledgements

Support was provided by the US National Institutes of Health, National Institute of General Medical Sciences (R01 GM103558-06) and gifts from Merck, AbbVie and Bristol-Myers Squibb.

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Twilton, J., Le, C., Zhang, P. et al. The merger of transition metal and photocatalysis. Nat Rev Chem 1, 0052 (2017). https://doi.org/10.1038/s41570-017-0052

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