Divergent Catalysis: Catalytic Asymmetric [4+2] Cycloaddition of Palladium Enolates
Kaylin N. Flesch, Alexander Q. Cusumano, Peng–Jui Chen, Christian Santiago Strong, Stephen R. Sardini, Yun E. Du, Michael D. Bartberger, William A. Goddard, Brian M. Stoltz
Abstract
An asymmetric decarboxylative [4+2] cycloaddition from a catalytically generated chiral Pd enolate was developed, forging four contiguous stereocenters in a single transformation. This was achieved through a strategy termed divergent catalysis, wherein departure from a known catalytic cycle enables novel reactivity of a targeted intermediate prior to re-entry into the original cycle. Mechanistic studies including quantum mechanics calculations, Eyring analysis, and KIE studies offer insight into the reaction mechanism.
Topics & Concepts
ChemistryCycloadditionStereocenterCatalysisCatalytic cyclePalladiumReactivity (psychology)Computational chemistryReaction mechanismCombinatorial chemistryEnantioselective synthesisOrganic chemistryMedicineAlternative medicinePathologyAsymmetric Synthesis and CatalysisAsymmetric Hydrogenation and CatalysisCatalytic C–H Functionalization Methods