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 5 a endowed with N-phthalimido tert-leucine paddlewheel ligands rather than by its homobimetallic dirhodium analogue 1 a. This virtue is likely the result of two synergizing factors: the conical shape of 5 a 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 of the ligand sphere.
['Collins|Lee R|LR|', 'Auris|Sebastian|S|', 'Goddard|Richard|R|', 'Fürstner|Alois|A|http://orcid.org/0000-0003-0098-3417']
cyclopropanation bimetallic catalysts bismuth carbene complexes rhodium