Phosphine-Catalyzed Synthesis of 6-Substituted 2-Pyrones: Manifestation of <i>E</i>/<i>Z</i>-Isomerism in the Zwitterionic Intermediate

Abstract

[reaction: see text] We report a one-step phosphine-catalyzed annulation between aldehydes and ethyl allenoate to form 6-substituted 2-pyrones. The mechanistic rationale for this reaction requires explicit discussion of the E/Z-isomerism of the zwitterionic intermediate formed by the addition of a phosphine to the allenoate. Sterically demanding trialkylphosphines facilitate the shift of equilibrium toward the E-isomeric zwitterion and lead to the formation of 6-substituted 2-pyrones. Various aromatic as well as aliphatic aldehydes undergo the transformation in moderate to excellent yield.