Orthogonal Selectivity in C–H Olefination: Synthesis of Branched Vinylarene with Unactivated Aliphatic Substitution

Oxidative coupling is a useful tool to synthesize vinylarenes. Despite remarkable successes in linear vinylarene, branched vinylarene synthesis has remained underdeveloped. Overcoming this limitation, herein, we report a chelation-assisted oxidative coupling to generate branched olefinated product in high yield. Exclusive branched selectivity was obtained using alkenyl carboxylic acid. Detailed experimental studies combined with computational investigations suggest that beta-migratory insertion, followed by a decarboxylation pathway is operative for the overall transformation.