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Asymmetric Carbene‐Catalyzed Oxidation of Functionalized Aldimines as 1,4‐Dipoles
Author(s) -
Wang Guanjie,
Zhang QiaoChu,
Wei Chenlong,
Zhang Ye,
Zhang Linxue,
Huang Juhui,
Wei Donghui,
Fu Zhenqian,
Huang Wei
Publication year - 2021
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.202017017
Subject(s) - aldimine , carbene , organocatalysis , catalysis , chemistry , enantioselective synthesis , enantiomer , combinatorial chemistry , substrate (aquarium) , enantiomeric excess , isatin , organic chemistry , oceanography , geology
The use of functionalized aldimines has been demonstrated as newly structural 1,4‐dipole precursors under carbene catalysis. More importantly, enantiodivergent organocatalysis has been successfully developed using carbene catalysts with the same absolute configuration, leading to both ( R )‐ and ( S )‐ enantiomers of six‐membered heterocycles with quaternary carbon centers. This strategy features a broad substrate scope, mild reaction conditions, and good enantiomeric ratio. DFT calculation results indicated that hydrogen bond C−H⋅⋅⋅F interactions between the catalyst and substrate are the key factors for controlling and even switching the enantioselectivity. These new 1,4‐dipoles can also react with isatin and its imines under carbene catalysis, allowing for access to the spiro oxindoles with excellent enantiomeric ratios.