American Chemical Society
ol8b02893_si_001.pdf (3.4 MB)

Intermolecular Reductive Couplings of Arylidene Malonates via Lewis Acid/Photoredox Cooperative Catalysis

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journal contribution
posted on 2018-10-21, 18:30 authored by Benjamin R. McDonald, Karl A. Scheidt
A cooperative Lewis acid/photocatalytic reduction of arylidene malonates yields a versatile radical anion species. This intermediate preferentially undergoes intermolecular radical–radical coupling reactions, and not the conjugate addition–dimerization reactivity typically observed in the single-electron reduction of conjugate acceptors. Reported here is the development of this open-shell species in intermolecular radical–radical cross couplings, radical dimerizations, and transfer hydrogenations. This reactivity underscores the enabling modularity of cooperative catalysis and demonstrates the utility of stabilized enoate-derived radical anions in intermolecular bond forming reactions.