Palladium-Catalyzed Asymmetric Decarboxylative [4+2] Dipolar Cycloaddition of 4-Vinyl-1,3-dioxan-2-ones with α,β-Disubstituted Nitroalkenes Enabled by a Benzylic Substituted P,N-Ligand
Juan Du, Yuanda Hua, Yang-Jie Jiang, Shuai Huang, Di Chen, Chang‐Hua Ding, Xue‐Long Hou
Abstract
The Pd-catalyzed asymmetric [4+2] cycloaddition reaction of an aliphatic 1,4-dipole with singly activated electron-deficient alkenes is realized for the first time, enabled by using a newly developed benzylic substituted P,N-ligand, affording tetrahydropyrans having three continuous chiral centers in high yields with high diastereo- and enantioselectivities. The rational transition states of the reaction as well as the role of the benzylic chiral center are proposed.
Topics & Concepts
ChemistryLigand (biochemistry)CatalysisCycloadditionPalladiumCombinatorial chemistry1,3-Dipolar cycloadditionMedicinal chemistryStereochemistryOrganic chemistryReceptorBiochemistryCatalytic C–H Functionalization MethodsCyclopropane Reaction MechanismsSynthesis and Catalytic Reactions