Palladium/Norbornene-Catalyzed ortho-Alkoxycarbonylation of Aryl Iodides Enabled Directly by Chloroformates

We present a palladium/norbornene-catalyzed ortho-alkoxycarbonylation of aryl iodides utilizing simple chloroformates as efficient alkoxycarbonyl sources, enabling concomitant ipso-functionalization encompassing alkenylation, cyanation, hydrogenation, and arylation. This methodology addresses fundamental limitations of conventional approaches by eliminating the necessity for preactivated reagents, demonstrating improved atom economy, and accommodating a broad spectrum of substrates, including both electron-rich and electron-deficient aryl iodides, diverse olefin terminators, and structurally complex or chiral chloroformates. Notably, the reaction employs a novel indolylphosphine ligand, which has been demonstrated to be essential for achieving enhanced reactivity and selectivity under mild conditions.