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Combinatorial Strategies to find New Catalysts for Asymmetric Hydrogenation Based on the Versatile Coordination Chemistry of METAMORPhos Ligands
Author(s) -
Terrade Frédéric G.,
Kluwer Alexander M.,
Detz Remko J.,
Abiri Zohar,
van der Burg Alida M.,
Reek Joost N. H.
Publication year - 2015
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.201500621
Subject(s) - chemistry , bimetallic strip , catalysis , ligand (biochemistry) , chirality (physics) , selectivity , combinatorial chemistry , asymmetric hydrogenation , stereochemistry , enantioselective synthesis , organic chemistry , biochemistry , chiral symmetry breaking , receptor , physics , quantum mechanics , nambu–jona lasinio model , quark
To extend the toolbox and find improved catalysts, anionic METAMORPhos ligands and neutral amino‐acid‐based ligands were used separately and in mixtures to form Rh complexes used in the asymmetric hydrogenation of eight industrially relevant substrates. Spectroscopic studies showed that under the catalytic conditions, the mononuclear complex with two different ligands (the heterocombination) is the main complex in solution if both the anionic and neutral ligands have the same chirality. If the neutral ligand and the anionic ligand have the opposite chirality at the P atom, monometallic and bimetallic heterocomplexes were detected by NMR spectroscopy and MS. For the majority of substrates evaluated in this study, higher enantioselectivities were obtained if the complexes used were based on the heterocombination of an anionic and a neutral ligand compared to respective homocombinations. After we found the initial leads, higher turnover numbers and enantioselectivities could be obtained easily by further exploring focused ligand libraries. The superior activity of the complexes based on the different ligands is highlighted by their robustness: significant divergence from a 1:1 ratio between the ligands does not lower the selectivity of the catalyst, although more of the competing homocomplexes are formed under these conditions.

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