Ni-Catalyzed Enantioselective Intermolecular Hydroamination of Branched 1,3-Dienes Using Primary Aliphatic Amines Gaël Tran Wen Shao Clément Mazet 10.1021/jacs.9b07253.s001 https://acs.figshare.com/articles/journal_contribution/Ni-Catalyzed_Enantioselective_Intermolecular_Hydroamination_of_Branched_1_3-Dienes_Using_Primary_Aliphatic_Amines/9770462 A Ni-catalyzed intermolecular enantioselective hydroamination of branched 1,3-dienes is reported. The method is broadly applicable, highly regio-, chemo-, and enantioselective, and provides direct access to valuable chiral allylic amines starting from linear or α-branched aliphatic primary amines or secondary amines. Mechanistic studies have been conducted using <sup>31</sup>P NMR spectroscopy for reaction progress monitoring, isotopic labeling experiments (<sup>2</sup>H), and kinetic analysis. The resting state of the catalyst is a Ni−π-allyl complex, and the outer-sphere nucleophilic attack of H-bonded amine aggregates is proposed to be the rate-determining step. This hypothesis guided the identification of an improved set of reaction conditions for the enantioselective hydroamination of branched 1,3-dienes. 2019-09-04 19:35:02 outer-sphere nucleophilic attack diene Primary Aliphatic Amines H-bonded amine aggregates chiral allylic amines enantioselective hydroamination reaction progress monitoring 31 P NMR spectroscopy Ni-Catalyzed Enantioselective Intermolecular Hydroamination