Ligand-controlled palladium-catalyzed regiodivergent aminocarbonylation of tert-alcohols†

Alcohols are widely available, abundant, and diverse in both commercial and natural resources. They possess low toxicity, making their use as reactants for carbonylation extremely promising. Herein, we present a robust ligand-controlled regioselective aminocarbonylation of tert-alcohols. Utilizing a commercially available palladium salt and ligand as the catalytic system, various amides containing an α-quaternary carbon or β-substituted amides can be selectively accessible. Notably, water is the only by-product of this reaction, which is consistent with the concept of green chemistry. This protocol offers a broad substrate scope, high regioselectivity, and excellent performance in scale-up reactions.