Palladium-Catalyzed Benzylic-Selective Hydroaminocarbonylation of Internal Alkenes.

Owing to the low reactivity of internal alkenes, their hydrocarbonylation is largely confined to isomerization-hydrocarbonylation reactions. Herein, a palladium-catalyzed benzylic-selective hydroaminocarbonylation of internal alkenes with aniline hydrochlorides is reported. A broad range of internal alkenes and anilines are compatible with the reaction, affording α-aryl carboxylic amides in high yields with high regioselectivity. The synthetic utility is illustrated by the gram-scale synthesis and concise preparation of key pharmaceutical intermediates and bioactive molecules.