Palladium-Catalyzed Decarboxylative Alkynylation of alpha-Acyloxyketones by C(sp(3))-O Bond Cleavage

Palladium-catalyzed decarboxylative alkynylation of alpha-acyloxyketones triggered by C(sp(3))-O bond cleavage is disclosed. The decarboxylation strategy featuring a neutral reaction condition enabled an unprecedent catalytic alkynylation of a ketone enolate. The reaction was applied to a variety of substrates, giving desired products in good yields. We successfully obtained X-ray crystallography of a new palladium-enolate intermediate that was synthesized by a reaction of [Pd(cod)(CH2TMS)(2)] with XPhos and alpha-acyloxyketone at room temperature, indicating facile C(sp(3))-O bond disconnection.