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Axially Chiral Dibenzazepinones by a Palladium(0)‐Catalyzed Atropo‐enantioselective C−H Arylation
Author(s) -
Newton Christopher G.,
Braconi Elena,
Kuziola Jennifer,
Wodrich Matthew D.,
Cramer Nicolai
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.201806527
Subject(s) - enantioselective synthesis , racemization , chirality (physics) , palladium , axial chirality , steric effects , surface modification , kinetic resolution , chemistry , catalysis , yield (engineering) , combinatorial chemistry , axial symmetry , stereochemistry , materials science , organic chemistry , physics , chiral symmetry breaking , quantum mechanics , nambu–jona lasinio model , metallurgy , quark
Atropo‐enantioselective C−H functionalization reactions are largely limited to the dynamic kinetic resolution of biaryl substrates through the introduction of steric bulk proximal to the axis of chirality. Reported herein is a highly atropo‐enantioselective palladium(0)‐catalyzed methodology that forges the axis of chirality during the C−H functionalization process, enabling the synthesis of axially chiral dibenzazepinones. Computational investigations support experimentally determined racemization barriers, while also indicating C−H functionalization proceeds by an enantio‐determining CMD to yield configurationally stable eight‐membered palladacycles.