Mechanistic insights in gold-stabilized nonclassical carbocations: Gold-catalyzed rearrangement of 3-cyclopropyl propargylic acetates

Article abstract of DOI:10.1021/ja909013j

The reaction of 3-cyclopropyl propargylic carboxylates with Au(I) and Au(III) catalysts affords selectively 5-(E)-alkylidenecyclopentenyl acetates via [3,3]-sigmatropic rearrangement of the carboxylic moiety followed by cyclopropyl ring opening and cyclization. DFT calculations have been performed, supporting a two-step no-intermediate mechanism along the cyclization coordinate. The stereoselective formation of the exocyclic alkenes is kinetically controlled in the first of these events. Although stereospecific in nature through a gold-stabilized nonclassical carbocation, the chirality transfer in these cyclopentannulations is not complete. Computational and experimental evidence is provided for a Au-promoted cyclopropyl ring opening/epimerization/ring closure in both cis- and trans-cyclopropyl settings, which competes with the cyclization event, thus eroding the stereochemical information transfer. When tertiary acetates were used, products of both 1,2- and 1,3-acyloxy migration processes could be isolated, supporting the competitive coexistence of these two pathways along the reaction profile, as suggested also by DFT calculations.