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Synthesis of Rhodium Complexes with Chiral Diene Ligands via Diastereoselective Coordination and Their Application in the Asymmetric Insertion of Diazo Compounds into E−H Bonds
Author(s) -
Ankudinov Nikita M.,
Chusov Denis A.,
Nelyubina Yulia V.,
Perekalin Dmitry S.
Publication year - 2021
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.202105179
Subject(s) - chemistry , rhodium , ligand (biochemistry) , oxazoline , enantiomer , diene , stereoselectivity , diazo , catalysis , chiral ligand , stereochemistry , enantioselective synthesis , enantiomeric excess , medicinal chemistry , combinatorial chemistry , organic chemistry , biochemistry , natural rubber , receptor
A new method for the synthesis of chiral diene rhodium catalysts is introduced. The readily available racemic tetrafluorobenzobarrelene complexes [(R 2 ‐TFB)RhCl] 2 were separated into two enantiomers via selective coordination of one of them with the auxiliary S ‐salicyl‐oxazoline ligand. One of the resulting chiral complexes with an exceptionally bulky diene ligand [( R , R ‐ i Pr 2 ‐TFB)RhCl] 2 was an efficient catalyst for the asymmetric insertion of diazoesters into B−H and Si−H bonds giving the functionalized organoboranes and silanes with high yields (79–97 %) and enantiomeric purity (87–98 % ee ). The stereoselectivity of separation via auxiliary ligand and that of the catalytic reaction was predicted by DFT calculations.