Formate-mediated reductive cross-couplings of vinyl halides with aryl iodides via palladium(I) catalysis occur with highly uncommon -substitution. The active dianionic palladium(I) catalyst, [PdI][NBu], is generated from Pd(OAc), BuNI, and formate. Oxidative addition of aryl iodide followed by dissociation of the dimer provides the monomeric anionic T-shaped arylpalladium(II) species, [Pd(Ar)(I)(NBu)], which, upon vinyl halide carbopalladation, forms products of -substitution by way of palladium(IV) carbenes, as corroborated by deuterium-labeling experiments.
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