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.

Abstract

A new method for the synthesis of chiral diene rhodium catalysts is introduced. The readily available racemic tetrafluorobenzobarrelene complexes [(R2 -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-iPr2 -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.