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Chiral Phosphate in Rhodium‐Catalyzed Asymmetric [2+2+2] Cycloaddition: Ligand, Counterion, or Both?
Author(s) -
Barbazanges Marion,
Caytan Elsa,
Lesage Denis,
Aubert Corinne,
Fensterbank Louis,
Gandon Vincent,
Ollivier Cyril
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601188
Subject(s) - rhodium , counterion , bimetallic strip , cycloaddition , chemistry , catalysis , ligand (biochemistry) , stereoselectivity , medicinal chemistry , phosphate , mass spectrometry , stereochemistry , organic chemistry , ion , biochemistry , receptor , chromatography
Investigations based on NMR spectroscopy, mass spectrometry, and DFT calculations shed light on the metallic species generated in the rhodium‐catalyzed asymmetric [2+2+2] cycloaddition reaction between diynes and isocyanates with the chiral phosphate TRIP. The catalytic mixture comprising [{Rh(cod)Cl} 2 ], 1,4‐diphenylphosphinobutane (dppb), and Ag( S )‐TRIP actually gives rise to two species, both having an effect on the stereoselectivity. One is a rhodium(I) complex in which TRIP is a weakly coordinating counterion, whereas the other is a bimetallic Rh/Ag complex in which TRIP is a strongly coordinating X‐type ligand.