Premium
Radical Changes in Lewis Acid Catalysis: Matching Metal and Substrate
Author(s) -
Bleith Tim,
Deng QingHai,
Wadepohl Hubert,
Gade Lutz H.
Publication year - 2016
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.201603072
Subject(s) - chemistry , catalysis , electrophile , selectivity , lewis acids and bases , metal , combinatorial chemistry , substrate (aquarium) , alkylation , organic chemistry , oceanography , geology
Whereas the stereochemical rigidity of the coordination sphere of boxmi/Cu II catalysts is key to achieving high enantioselectivity in the electrophilic alkylation of β‐ketoesters, this pathway is outperformed by a radical process for the corresponding catalytic transformation of oxindoles, giving rise to racemic products. For the corresponding Zn II catalysts, the selectivity in the latter process is outstanding despite the greater plasticity of the coordination shell. This reaction was thus developed into a highly useful synthetic method, which enabled the conversion of wide range of substrates with high yields and enantioselectivities.