Phosphine-catalyzed synthesis of 6-substituted 2-pyrones: manifestation of E/Z-isomerism in the zwitterionic intermediate.
[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.
Department of Chemistry and Biochemistry, University of California, Los Angeles, 90095-1569, USA.
Xue-Feng
XF
Zhu
Arnaud-Pierre
AP
Schaffner
Ronald C
RC
Li
Ohyun
O
Kwon