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Asymmetric hydrogenation of γ ‐branched allylamines for the efficient synthesis of γ ‐chirogenic amines
Author(s) -
Zhang Jian,
Chen Tiantian,
Wang Yuanhao,
Zhou Fengfan,
Zhang Zhenfeng,
Gridnev Ilya D.,
Zhang Wanbin
Publication year - 2021
Publication title -
natural sciences
Language(s) - English
Resource type - Journals
ISSN - 2698-6248
DOI - 10.1002/ntls.10021
Subject(s) - chemistry , asymmetric hydrogenation , amine gas treating , chelation , catalysis , catalytic hydrogenation , combinatorial chemistry , organic chemistry , enantioselective synthesis , stereochemistry
The efficient construction of γ ‐chirogenic amines has been realized via asymmetric hydrogenation of γ ‐branched N ‐phthaloyl allylamines by using a bisphosphine‐Rh catalyst bearing a large bite angle. The desired products possessing different γ ‐substituents were obtained in quantitative yields and with excellent enantioselectivities (up to >99% ee). This protocol provides a practical method for the preparation of γ ‐chirogenic amine derivatives such as the famous antidepressant drug Fluoxetine (up to 50000 S/C). The mechanistic calculations show an unusual P‐Rh‐P trans ‐chelating pattern and a weak interaction‐promoted activation mode which are completely different from the traditional cis ‐chelating pattern and coordination‐promoted activation mode in metal‐catalyzed hydrogenations. Key points Novel methodology of asymmetric hydrogenation was developed for efficient synthesis of γ‐chirogenic amines. New synthetic route was developed for the well‐known antidepressant drug Fluoxetine. Unusual mechanism information was found in the bidentate bisphosphine‐Rh‐catalyzed hydrogenation.

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