ProPhenol Derived Ligands to Simultaneously Coordinate a Main‐Group Metal and a Transition Metal: Application to a Zn−Cu Catalyzed Reaction
Barry M. Trost, Guoting Zhang, Minghao Xu, Xiaotian Qi
Abstract
Abstract A new bifunctional ligand bearing chiral N‐heterocyclic carbene (NHC) and prolinol moieties is presented. Utilizing the designed ligand, an in situ formed Cu/Zn hetero‐bimetallic complex unlocks the asymmetric allylic alkylation reactions of allyl phosphates with zinc keto‐homoenolates, leading to the formation of various γ‐vinyl ketones with good regio‐ and enantio‐selectivity. DF sT calculation supports that the chelation of allyl phosphates with catalyst promotes the S N 2’ addition and the ligand‐substrate steric interactions account for the stereoselective outcome.
Topics & Concepts
ChemistryBimetallic stripLigand (biochemistry)Allylic rearrangementCatalysisBifunctionalCarbeneSteric effectsStereoselectivityTransition metalTsuji–Trost reactionChelationSubstrate (aquarium)ZincMedicinal chemistryAlkylationCombinatorial chemistryStereochemistryOrganic chemistryReceptorGeologyBiochemistryOceanographyN-Heterocyclic Carbenes in Organic and Inorganic ChemistryCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization Methods