Synthesis of 4-Pyrones by Formal Hydration of 1,3-Diynones Promoted by 1,4-Addition of Piperidine

A new approach for the synthesis of 4-pyrones with broader substrate scope and functional group tolerance is described. The reaction proceeds via an initial 1,4-addition by piperidine, followed by nitrogen-assisted 6-endo-dig cyclization and hydrolysis. 1,3-Diynones with nonenolizable electron-withdrawing ketones and nonpropargylic H provide relatively high yields. For substrates with particular R2 substituents, 1,4- or 1,6-adducts were isolated, suggesting that steric and electronic factors of the R2 substituent should have a strong impact on the 6-endo-dig cyclization.