62. Ni-Catalyzed Enantioselective Intermolecular Hydroamination of Branched 1,3-Dienes Using Primary Aliphatic Amines
    Gaël Tran, Wen Shao, Clément Mazet*
    J. Am. Chem. Soc. 2019, 141, 14814-14822

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 ³¹P NMR spectroscopy for reaction progress monitoring, isotopic labeling experiments (2H) 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.

archive ouverte unige:123450

DOI de la version éditeur : 10.1021/jacs.9b07253 

DOI de l'AAM : 10.26037/yareta:c4y44m4cjzhgbnhlx2kycfyetu 

DOI du Dataset : 10.26037/yareta:xq7btypwvfbzvafosdb4exo4ga