Substrate Plasticity Enables Group-Selective Transmetalation: Catalytic Stereospecific Cross-Couplings of Tertiary Boronic Esters
Hao Liang, James P. Morken
Abstract
Activation of enantiomerically enriched tertiary alkylboronic esters with adamantyllithium generated in situ enables stereoretentive boron-to-copper transmetalation. The resulting alkylcopper species can undergo cross-coupling reactions with an array of electrophiles to furnish synthetically useful compounds bearing quaternary stereocenters. DFT calculations of the transmetalation process provide insights for reactivity and selectivity.
Topics & Concepts
TransmetalationChemistryStereocenterElectrophileStereospecificityReactivity (psychology)SelectivitySubstrate (aquarium)Combinatorial chemistryBoronBoronic acidHydroborationOrganic chemistryCatalysisEnantioselective synthesisMedicineOceanographyAlternative medicineGeologyPathologyOrganoboron and organosilicon chemistryCatalytic Cross-Coupling ReactionsCoordination Chemistry and Organometallics