Design and Synthesis of Chiral Heteroleptic Rhodium(II) Carboxylate Catalysts: Experimental Investigation of Halogen Bond Rigidification Effects in Asymmetric Cyclopropanation

A general method for the synthesis of chiral heteroleptic rhodium(II) tetracarboxylate catalysts is reported. The chlorinated TCPT unit was found to be an efficient polarity-control group, allowing the isolation of each complex from a mixture of six possible products. This approach contributes to enlarging the scope of accessible chiral Rh(II) catalysts and allowed further study of the halogen bond rigidification effect observed in chlorinated complexes.