Domino Synthesis of 2,3-Dialkylidenetetrahydrofurans via Tandem Prins Cyclization-Skeletal Reorganization.

A domino synthesis of 2,3-dialkylidenetetrahydrofurans based on Prins-type cyclization of 3,5-diynols and aldehydes is described. In the present reaction, skeletal reorganization of the Prins-cyclized intermediates proceeds via a ring-opening reaction followed by intramolecular (hemi)acetalization of the resulting 4-en-1-yn-3-ones. Furthermore, a representative product undergoes a Diels-Alder reaction with dimethyl acetylenedicarboxylate (DMAD) to afford a highly substituted 2,3-dihydrobenzofuran.