Palladium-catalysed branch- and enantioselective allylic C–H alkylation of ?-alkenes

Enantioselective functionalization of alkenes is an attractive and straightforward method to assemble molecular complexity from readily available chemical feedstocks. Although regio- enantioselective transformations the C=C bond have been extensively studied, those allylic C–H bonds unactivated are yet be explored. Here we report a palladium-catalysed branch- alkylation that capable accommodating diverse types ?-alkenes, ranging feedstocks annually manufactured on million-tonne scale olefins tethering wide scope appended functionalities, providing unconventional access chiral ?,?-unsaturated amides. Notably, mechanistic studies reveal regioselectivity not only governed by coordination pattern nucleophiles but also regulated ligational behaviours ligands, highlighting importance monoligation phosphoramidite ligands in provoking high levels stereo- branch-selectivity via nucleophile coordination-enabled inner-sphere allylation pathway. The selective well however, relatively underexplored. Now, branch-selective C?H ?-alkenes reported. process tolerates range bioactive