Gold-catalyzed reactivity of 3-silyloxy-1,5-enynes: a synthetic tool for the synthesis of complex structures and its limitations

Gold-catalyzed reactions of 3-silyloxy-1,5-enynes in the presence of sterically demanding alcohols afford 4-acylcyclopentenes. The cascade process most likely proceeds through a 6-endo-dig carbocyclization and subsequent pinacol-type rearrangement. Studies that define scope and limitations of the cyclization–migration strategy are also described. An alternative cascade yields highly substituted aryls through an unprecedented cyclization–fragmentation pathway.