title: Radical Changes in Lewis Acid Catalysis: Matching Metal and Substrate.
abstract: 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.
authors.affiliation: Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
authors.forename: Tim
authors.initials: T
authors.lastname: Bleith
authors.affiliation: Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.|The Education Ministry Key Lab of Resource Chemistry and Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, Shanghai, 200234, P.R. China.
authors.forename: Qing-Hai
authors.initials: QH
authors.lastname: Deng
authors.affiliation: Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
authors.forename: Hubert
authors.initials: H
authors.lastname: Wadepohl
authors.affiliation: Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany. lutz.gade@uni-hd.de.
authors.forename: Lutz H
authors.initials: LH
authors.lastname: Gade
keywords: copper; enantioselective catalysis; radical reactions; reaction mechanisms; zinc