Chiral Heterobimetallic Bismuth–Rhodium Paddlewheel Catalysts: A Conceptually New Approach to Asymmetric Cyclopropanation
Dr. Lee R. Collins
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany
Search for more papers by this authorSebastian Auris
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany
Search for more papers by this authorDr. Richard Goddard
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany
Search for more papers by this authorCorresponding Author
Prof. Alois Fürstner
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany
Search for more papers by this authorDr. Lee R. Collins
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany
Search for more papers by this authorSebastian Auris
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany
Search for more papers by this authorDr. Richard Goddard
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany
Search for more papers by this authorCorresponding Author
Prof. Alois Fürstner
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany
Search for more papers by this authorDedicated to Professor Walter Thiel on the occasion of his 70th birthday
Graphical Abstract
Stretched and Bent: Formal replacement of one Rh atom in a classical dirhodium tetracarboxylate paddlewheel complex by Bi results in a conical shape of the precatalyst: while the wide-open Bi site does not cause a racemic background reaction, the calyx-like chiral binding pocket around Rh is narrower and hence more effective. These two virtues likely synergize in asymmetric cyclopropanation reactions.
Abstract
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.
Supporting Information
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