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Site‐ and Enantioselective C−H Oxygenation Catalyzed by a Chiral Manganese Porphyrin Complex with a Remote Binding Site
Author(s) -
Burg Finn,
Gicquel Maxime,
Breitenlechner Stefan,
Pöthig Alexander,
Bach Thorsten
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.201712340
Subject(s) - enantioselective synthesis , chemistry , catalysis , manganese , selectivity , porphyrin , yield (engineering) , substrate (aquarium) , photochemistry , combinatorial chemistry , stereochemistry , organic chemistry , materials science , oceanography , metallurgy , geology
A chiral manganese porphyrin complex with a two‐point hydrogen‐bonding site was prepared and probed in catalytic C−H oxygenation reactions of 3,4‐dihydroquinolones. The desired oxygenation occurred with perfect site selectivity at the C4 methylene group and with high enantioselectivity in favor of the respective 4 S ‐configured secondary alcohols (12 examples, 29–97 % conversion, 19–68 % yield, 87–99 % ee ). Mechanistic studies support the hypothesis that the reaction proceeds through a rate‐ and selectivity‐determining attack of the reactive manganese oxo complex at the hydrogen‐bound substrate and an oxygen transfer by a rebound mechanism.