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Enantiotopos‐Selective CH Oxygenation Catalyzed by a Supramolecular Ruthenium Complex
Author(s) -
Frost James R.,
Huber Stefan M.,
Breitenlechner Stefan,
Bannwarth Christoph,
Bach Thorsten
Publication year - 2015
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.201409224
Subject(s) - ruthenium , catalysis , enantioselective synthesis , substrate (aquarium) , chemistry , porphyrin , photochemistry , ring (chemistry) , hydrogen bond , stereochemistry , combinatorial chemistry , molecule , organic chemistry , oceanography , geology
Spirocyclic oxindoles undergo an enantioselective oxygenation reaction (nine examples; e.r. up to 97:3) upon catalysis by a chiral ruthenium porphyrin complex (1 mol %). The catalyst exhibits a lactam ring, which is responsible for substrate association through hydrogen bonds, and an active ruthenium center, which is in a defined spatial relationship to the oxygenation substrate. DFT calculations illustrate the perfect alignment of the active site with the reactive CH bond and suggest—in line with the kinetic isotope effect—an oxygen rebound mechanism for the reaction.