The cyclization of o-hydroxyphenyl ethynyl ketones was examined from theoretical and experimental standpoints in order to develop efficient synthetic methods for the construction of 2-substituted pyranones possessing significant biological activities. Ab initio studies at HF/6–31G∗ level on the cyclization indicated that both 6-endo-digonal and 5-exo-digonal cyclizations giving benzopyranones and benzofuranones, respectively, were endothermic ...