Enantiodivergent Intermolecular Hydroamination of Acyclic 1,3-Dienes Using Aniline Nucleophiles

Abstract

Enantioselective hydroamination of acyclic conjugated dienes represents a straightforward approach to the synthesis of chiral allylic amines. While recent advances have demonstrated remarkable regio- and enantioselectivity for a range of N-nucleophiles, the development of methodologies for the less reactive aniline derivatives remains underexplored. Here, we report an enantiodivergent strategy for intermolecular hydroamination of acyclic 1,3-dienes using aniline nucleophiles. This Pd-catalyzed protocol employs an anthracene photodimer-derived monophosphine ligand and achiral acids as the essential additive, producing highly regioselective and enantio-enriched products with good substrate scope. Notably, variation of acid additives induces controlled inversion of the products’ absolute configuration.