Asymmetric Markovnikov Hydroamino­carbonylation of Alkenes Enabled by Palladium-Monodentate Phosphoramidite Catalysis

A palladium-catalyzed asymmetric Markovnikov hydroamino­carbonylation of alkenes with anilines has been developed for the atom-economical synthesis of 2-substituted propan­amides bearing an α-stereo­center. A novel phosphor­amidite ligand L16 was discovered which exhibited very high reactivity and selectivity in the reaction. This asymmetric Markovnikov hydroamino­carbonylation employs readily available starting materials and tolerates a wide range of functional groups, thus providing a facile and straightforward method for the regio- and enantio­selective synthesis of 2-substituted propan­amides under ambient conditions. Mechanistic studies revealed that the reaction proceeds through a palladium hydride pathway.