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Publication 62  

  1. 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.

open archive unige:123450

Editor’s version DOI: 10.1021/jacs.9b07253 

AAM DOI: 10.26037/yareta:c4y44m4cjzhgbnhlx2kycfyetu 

Dataset DOI: 10.26037/yareta:xq7btypwvfbzvafosdb4exo4ga