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Dynamic Kinetic Resolution of Heterobiaryl Ketones by Zinc‐Catalyzed Asymmetric Hydrosilylation
Author(s) -
Hornillos Valentín,
Carmona José A.,
Ros Abel,
IglesiasSigüenza Javier,
LópezSerrano Joaquín,
Fernández Rosario,
Lassaletta José M.
Publication year - 2018
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.201713200
Subject(s) - kinetic resolution , chemistry , bifunctional , enantioselective synthesis , hydrosilylation , ketone , stereocenter , chirality (physics) , axial chirality , stereospecificity , lewis acids and bases , zinc , catalysis , organic chemistry , stereochemistry , chiral symmetry breaking , physics , quantum mechanics , quark , nambu–jona lasinio model
A diastereo‐ and highly enantioselective dynamic kinetic resolution (DKR) of configurationally labile heterobiaryl ketones is described. The DKR proceeds by zinc‐catalyzed hydrosilylation of the carbonyl group, thus leading to secondary alcohols bearing axial and central chirality. The strategy relies on the labilization of the stereogenic axis that takes place thanks to a Lewis acid–base interaction between a nitrogen atom in the heterocycle and the ketone carbonyl group. The synthetic utility of the methodology is demonstrated through stereospecific transformations into either N , N ‐ligands or appealing axially chiral, bifunctional thiourea organocatalysts.