Chiral Heterobimetallic Bismuth-Rhodium Paddlewheel Catalysts: A Conceptually New Approach to Asymmetric Cyclopropanation.

Cyclopropanation reactions of styrene derivatives with donor/acceptor carbenes formed in situ are significantly more enantioselective when catalyzed by the heterobimetallic bismuth-rhodium complex 5a endowed with N-phthalimido tert-leucine paddlewheel ligands rather than by its homobimetallic dirhodium analogue 1a. This virtue is likely the result of two synergizing factors: the conical shape of 5a translates into a narrower calyx-like chiral binding site about the catalytically active Rh center; the Bi atom, although fully solvent exposed, does not decompose aryl diazoacetates and is hence incapable of promoting a racemic background reaction. Moreover, ligand variation proved that successful catalyst design mandates that the anisotropy of the conical heterobimetallic core be matched by proper directionality within the ligand sphere.