Publications > Fernández-García et al
Gold-Catalyzed Cycloisomerizations of Functionalyzed Cyclopropyl Alkynes: the Cases of Carboxamides and Alcohols
Palabras clave: Alkynes; gold; nucleophilic addition; ring expansion; seven-membered heterocycles; pyranones
Resumen
Push-pull alkynylcyclopropane derivatives are claimed as suitable and active substrates for gold-catalyzed transformations. Thus, 2(3H)-azepinones can be readily prepared from alkynylcyclopropanecarboxamides through a nucleophilic addition/cyclopropane ring-opening cascade process and, in this manuscript, the scope and the limitations of such reaction sequence are reported. The cascade reaction is general and occurs with complete regio- and quimioselection to form the seven-membered heterocycles with the exception of primary alkyl-substituted alkynylcyclopropanecarboxamides that render 4-methoxy-6-oxo-4-enenitriles in moderate yields. Additionally, less activated alkynylcyclopropylmethanols undergo regioselective cycloisomerization at low temperature leading to oxabicyclo%@5B4.1.0%@5Dheptanes. Notably, the cyclopropane ring opening of these adducts takes place under thermal conditions to form dihydropyranones.