Structure-Dependent, Switchable Alder-Ene/[2π + 2σ] Cycloadditions of Vinyl Bicyclo[1.1.0]butanes with α-Ketoesters Enabled by Palladium Catalysis
Wei Wang, Jun‐An Xiao, Lan Zheng, Wenjie Liang, Yang Liu, Xiao-Xiang Huang, Chenxiang Lin, Kai Chen, Wei Su, Hua Yang
Abstract
A structure-dependent, palladium-catalyzed switchable alder-ene/[2π + 2σ] cycloaddition of VBCBs with α-ketoesters has been reported. A variety of cyclobutenes and 2-oxabicyclo[2.1.1]hexanes have been efficiently achieved in good to excellent yields through strain-release-driven alder-ene reactions and [2π + 2σ] cycloadditions, respectively. The potential of this method is illustrated by the scale-up reaction and diverse postsynthetic transformations of the obtained cyclic scaffolds. Additionally, the reaction mechanism and origins of the chemoselectivity have been probed by computational studies.
Topics & Concepts
ChemistryChemoselectivityCycloadditionPalladiumEne reactionCatalysisBicyclic moleculeCombinatorial chemistryMedicinal chemistryOrganic chemistryStereochemistryCatalytic Alkyne ReactionsOxidative Organic Chemistry ReactionsSynthetic Organic Chemistry Methods