Gold-catalyzed hydrative carbocyclization of 1,5- and 1,6-diyn-3-ones via an oxygen transfer process.
This study reports new hydrative carbocyclizations of 1,5- and 1,6-diyn-3-ones catalyzed by PPh3AuOTf, involving a pi-alkyne-assisted oxygen transfer in the reaction mechanisms. Treatment of 2-(alk-2-yn-1-onyl)-1-alkynylbenzenes with PPh3AuOTf (5 mol %) in wet 1,4-dioxane (23 degrees 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.
Department of Chemistry, National Tsing-Hua University, Hsinchu, Taiwan, Republic of China.
Jhih-Meng
JM
Tang
Ting-An
TA
Liu
Rai-Shung
RS
Liu