Asymmetric Hydrogenation of γ -Branched Allylamines for the
Efficient Synthesis of γ -Chirogenic Amines
Jian Zhang,[a] Yuanhao
Wang,[a] Fengfan Zhou,[a]Zhenfeng Zhang,*[a] Ilya D.
Gridnev,*[c] and Wanbin
Zhang*[a,b]
Abstract: The efficient construction of γ -chirogenic
amines has been realized via asymmetric hydrogenation ofγ -branched N -phthaloyl allylamines by using a
bisphosphine-Rh catalyst bearing a large bite angle. The desired
products possessing different types of γ -substituents were
obtained in quantitative yields and with excellent enantioselectivities
(up to >99.9% ee). This protocol provided a practical
method for the preparation of γ -chirogenic amine derivatives such
as the famous antidepressant drug Fluoxetine (up to 50000 S/C). The
mechanism calculation shows a weak interaction-promoted activation mode
which is completely different from the traditional coordination-promoted
activation mode in the Rh-catalyzed hydrogenation.