Divergent Catalysis: Catalytic Asymmetric [4+2] Cycloaddition of Palladium Enolates
Kaylin N Flesch1, Alexander Q Cusumano1, Peng-Jui Chen1
1The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
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.
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