Published in:Angewandte Chemie International Edition
Language:
English
DOI:
10.1002/anie.201712340
ISSN:
1521-3773;
1433-7851
Origination:
Footnote:
Description:
<jats:title>Abstract</jats:title><jats:p>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<jats:italic>S</jats:italic>‐configured secondary alcohols (12 examples, 29–97 % conversion, 19–68 % yield, 87–99 % <jats:italic>ee</jats:italic>). 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.</jats:p>