A novel sequential reaction involving umpolung acetoxylation of a Pd enolate intermediate has been achieved. Cyclative diacetoxylation of alkynyl cyclohexadienones was promoted by Pd-SPRIX catalyst under an oxygen atmosphere to give densely functionalized benzofuranone derivatives in good yields. SPRIX was essential for the unusual nucleophilic interception of a Pd enolate by an acetate anion because no other ligands exhibited any positive effects. This reaction turned out to proceed enantioselectively by using optically pure SPRIX.

Umpolung reactivity of Pd enolate: Cyclative diacetoxylation of alkynyl cyclohexadienones catalyzed by Pd-SPRIX

245th National Meeting (2013)

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