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Mechanistic Insights into the Iridium‐Catalyzed Hydrogenations of α,β‐Unsaturated Ketones
Author(s) -
Engel Julien,
Mersmann Stefanie,
Norrby PerOla,
Bolm Carsten
Publication year - 2016
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201600730
Subject(s) - iridium , catalytic cycle , ligand (biochemistry) , chemistry , hydride , catalysis , metathesis , enantioselective synthesis , oxidation state , substrate (aquarium) , stereochemistry , medicinal chemistry , combinatorial chemistry , organic chemistry , polymerization , hydrogen , biochemistry , polymer , receptor , oceanography , geology
The highly enantioselective hydrogenation of linear enones catalyzed by Ir complexes that bear a chiral P,N ligand have been investigated computationally. Compared to the results of previous studies, the mechanism is different because of the coordination of the substrate. In the favored pathway Ir stays in the +3 oxidation state throughout the entire catalytic cycle, the olefinic group is coordinated trans to the ligand N atom, and the carbonyl group binds trans to a spectator hydride. After migratory insertion, a H 2 coordinates and delivers the second H atom by σ‐metathesis. The calculated path rationalizes the observed enantioselectivities and allows the development of a predictive quadrant model for this class of substrate–ligand combination.