Abstract
(Chemical Equation Presented) This study reports new hydrative carbocyclizations of 1,5- and 1,6-diyn-3-ones catalyzed by PPh 3 AuOTf, involving a π-alkyne-assisted oxygen transfer in the reaction mechanisms. Treatment of 2-(alk-2-yn-1-onyl)-1-alkynylbenzenes with PPh 3 AuOTf (5 mol %) in wet 1,4-dioxane (23°C, 10 min) led to hydrative aromatization to give 4-hydroxyl-1-naphthyl ketones efficiently. This approach is also extendible to the hydrative cyclization of acyclic 1,5-diyn-3-ones, which afforded 4-cyclopentenonyl ketones in reasonable yields. On the basis of this oxygen-labeling study, we propose a plausible mechanism involving an alkyne-assisted oxygen transfer to generate key oxonium and gold-enolate intermediates. © 2008 American Chemical Society.