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Ni-Catalyzed Enantioselective Intermolecular Hydroamination of Branched 1,3-Dienes Using Primary Aliphatic Amines
journal contribution
posted on 2019-09-04, 19:35 authored by Gaël Tran, Wen Shao, Clément MazetA 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.