Formate-Mediated Reductive Cross-Coupling of Vinyl Halides and Aryl Iodides: <i>cine</i>-Substitution via Palladium(I) Catalysis.

ABSTRACT: Formate-mediated reductive cross-couplings of vinyl halides with aryl iodides via palladium(I) catalysis occur with highly uncommon cine-substitution. The active dianionic palladium(I) catalyst, [Pd₂I₄][NBu₄]₂, is generated in situ from Pd(OAc)₂, Bu₄NI, 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)₂(NBu₄)], which, upon vinyl halide carbopalladation, forms products of cine-substitution by way of palladium(IV) carbenes, as corroborated by deuterium-labeling experiments.

SUBMITTER: Santana CG 

PROVIDER: S-EPMC11445720 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature