Biomimetic sulfur-catalyzed carbonyl transfer enables the carbonylative difunctionalization of unactivated alkenes

Novel organic synthesis platforms inspired by enzyme-promoted biochemical transformations often demonstrate unexpected efficacy in solving challenging problems in organic synthesis. Drawing inspiration from the acyl transfer process catalyzed by coenzyme A (CoA) and acetyl-CoA in living organisms, we have developed a biomimetic acyl transfer strategy catalyzed by organic sulfur compounds. By activating the inert C-F bonds of trifluoromethyl aromatics, a multi-component radical relay strategy enables the efficient construction of fluorine-modified γ-aryl carboxylic acid derivatives. Sulfur compounds serve dual roles in the catalytic cycle, acting as electron-donor catalysts to activate inert C-F bonds and forming thioester intermediates to transfer acyl groups to nucleophiles. Building upon this platform, we have for the first time extended the scope of fluoroalkyl carbon radical precursors in cascade carbonylation of alkenes from reactive species to unactivated trifluoromethylarenes.