Palladium-Catalyzed Enantioselective Cycloaddition of Carbonylogous 1,4-Dipoles: Efficient Access to Chiral Cyclohexanones
Barry M. Trost, Zhiwei Jiao
Abstract
A novel palladium-mediated carbonylogous 1,4-dipole was developed by in situ deprotonation. By using our own-developed C2-unsymmetric phosphoramidite as supporting ligand, this dipole was applied to the asymmetric synthesis of chiral cyclohexanones via a catalytic [4+2] cycloaddition. Electron-deficient allylic carbonate was used to generate the highly reactive palladium-mediated dipoles for the first time, and a diverse array of stable dipole precursors was explored for the elaboration of chiral cyclohexanones. A general mechanism for the reaction process and stereochemical outcome was proposed, which can be useful in designing and predicting future transformation.
Topics & Concepts
ChemistryPalladiumPhosphoramiditeEnantioselective synthesisCycloadditionAllylic rearrangementCatalysisDeprotonationDipoleLigand (biochemistry)Combinatorial chemistryComputational chemistryStereochemistryOrganic chemistryReceptorIonDNABiochemistryOligonucleotideCyclopropane Reaction MechanismsAsymmetric Synthesis and CatalysisCatalytic C–H Functionalization Methods