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Ligand‐Enabled Enantioselective C sp 3 –H Activation of Tetrahydroquinolines and Saturated Aza‐Heterocycles by Rh I
Author(s) -
Greßies Steffen,
Klauck Felix J. R.,
Kim Ju Hyun,
Daniliuc Constantin G.,
Glorius Frank
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.201805680
Subject(s) - enantioselective synthesis , chemistry , rhodium , ligand (biochemistry) , chemoselectivity , catalysis , combinatorial chemistry , denticity , stereochemistry , medicinal chemistry , organic chemistry , crystal structure , receptor , biochemistry
Abstract The first rhodium(I)‐catalyzed enantioselective intermolecular Csp3–H activation of various saturated aza‐heterocycles including tetrahydroquinolines, piperidines, piperazines, azetidines, pyrrolidines, and azepanes is presented. The combination of a rhodium(I) precatalyst and a chiral monodentate phosphonite ligand is shown to be a powerful catalytic system to access a variety of important enantio‐enriched heterocycles from simple starting materials. Notably, the Csp3–H activation of tetrahydroquinolines is especially challenging due to the adjacent Csp2−H bond. This redox‐neutral methodology provides a new synthetic route to α‐N‐arylated heterocycles with high chemoselectivity and enantioselectivity up to 97 % ee .