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