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

Article abstract of DOI:10.1002/anie.202105179

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.