A New Ligand Design Based on London Dispersion Empowers Chiral Bismuth–Rhodium Paddlewheel Catalysts
Santanu Singha, Michael Buchsteiner, Giovanni Bistoni, Richard Goddard, Alois Fürstner
Abstract
-positions of the aromatic ring exhibit outstanding levels of selectivity in reactions of donor/acceptor and donor/donor carbenes; at the same time, the reaction rates are much faster and the substrate scope is considerably wider than those of previous generations of chiral [BiRh] catalysts. As shown by a combined experimental, crystallographic, and computational study, the new catalysts draw their excellent application profile largely from the stabilization of the chiral ligand sphere by London dispersion (LD) interactions of the peripheral silyl substituents.
Topics & Concepts
ChemistryRhodiumBismuthCatalysisLigand (biochemistry)Dispersion (optics)Chirality (physics)SelectivitySubstrate (aquarium)AcceptorCoordination sphereCombinatorial chemistryStereochemistryMoleculeOrganic chemistryReceptorChiral symmetry breakingNambu–Jona-Lasinio modelCondensed matter physicsGeologyOpticsQuarkPhysicsQuantum mechanicsOceanographyBiochemistryCyclopropane Reaction MechanismsAsymmetric Hydrogenation and CatalysisCatalytic C–H Functionalization Methods