Synthesis and Structural Characterization of Stable Organogold(I) Compounds. Evidence for the Mechanism of Gold-Catalyzed Cyclizations

The vast majority of homogeneous Au-catalyzed reactions have exploited the propensity of Au to activate unsaturated carbon-carbon bonds as electrophiles. It is generally assumed that a nucleophile attacks a gold-activated carbon-carbon multiple bond to give an alkenyl Au intermediate, notwithstanding the fact that these intermediates are hitherto unknown. We have obtained room temperature stable gamma-lactone gold(I) complexes through the reaction of cationic Au(I) reagents with allenoates, under mild conditions. The reactions of one such complex with electrophiles yielded the expected products of Au-catalyzed cyclizations. These results furnish experimental evidence for the mechanism of Au-catalyzed cyclizations.