Highly efficient palladium‐catalyzed hydroesterification of functionalized alkenes

Herein, we introduce a catalytic system consisting of Pd (OAc) 2 /Xantphos/Al (OTf) 3 , which exhibits excellent reactivity in catalyzing the hydroesterification of a wide range of substrates, including electron‐deficient unsaturated acids/esters, aliphatic alkenes, functionalized styrenes, and phenylacetylenes. The catalytic system featured high reactivity and selectivity, low catalyst loading, wide substrate scope, and low CO pressure. Importantly, it eliminated the need for corrosive strong Brønsted acid additives, yielding alkyl‐ or aryl‐substituted dicarboxylic acid esters and monocarboxylic acid ester derivatives that hold significant industrial and pharmaceutical value. Mechanistic studies indicate that the reaction proceeds via the palladium hydride pathway.