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Rational Optimization of Supramolecular Catalysts for the Rhodium‐Catalyzed Asymmetric Hydrogenation Reaction
Author(s) -
Daubignard Julien,
Detz Remko J.,
Jans Anne C. H.,
de Bruin Bas,
Reek Joost N. H.
Publication year - 2017
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.201707670
Subject(s) - catalysis , chemistry , rhodium , rational design , combinatorial chemistry , hydrogen bond , substrate (aquarium) , selectivity , organic chemistry , materials science , molecule , nanotechnology , oceanography , geology
Rational design of catalysts for asymmetric transformations is a longstanding challenge in the field of catalysis. In the current contribution we report a catalyst in which a hydrogen bond between the substrate and the catalyst plays a crucial role in determining the selectivity and the rate of the catalytic hydrogenation reaction, as is evident from a combination of experiments and DFT calculations. Detailed insight allowed in silico mutation of the catalyst such that only this hydrogen bond interaction is stronger, predicting that the new catalyst is faster. Indeed, we experimentally confirmed that optimization of the catalyst can be realized by increasing the hydrogen bond strength of this interaction by going from a urea to phosphine oxide H‐bond acceptor on the ligand.