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SpinPhox/Iridium(I)‐Catalyzed Asymmetric Hydrogenation of Cyclic α‐Alkylidene Carbonyl Compounds
Author(s) -
Liu Xu,
Han Zhaobin,
Wang Zheng,
Ding Kuiling
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201309521
Subject(s) - enantioselective synthesis , asymmetric hydrogenation , iridium , chemistry , catalysis , optically active , enantiomer , combinatorial chemistry , enantiomeric excess , organic chemistry , stereochemistry
Optically active medium‐sized cyclic carbonyl compounds bearing an α‐chiral carbon center are of interest in pharmaceutical sciences and asymmetric synthesis. Herein, SpinPhox/Ir I catalysts have been demonstrated to be highly enantioselective in the asymmetric hydrogenation of the CC bonds in the exocyclic α,β‐unsaturated cyclic carbonyls, including a broad range of α‐alkylidene lactams, unsaturated cyclic ketones, and lactones. It is noteworthy that the procedure can be successfully used in the asymmetric hydrogenation of the challenging α‐alkylidenelactam substrates with six‐ or seven‐membered rings, thus affording the corresponding optically active carbonyl compounds with an α‐chiral carbon center in generally excellent enantiomeric excesses (up to 98 % ee ). Synthetic utility of the protocol has also been demonstrated in the asymmetric synthesis of the anti‐inflammatory drug loxoprofen and its analogue, as well as biologically important ε‐aminocaproic acid derivatives.