α-Carbonyl Cations in Sulfoxide-Driven Oxidative Cyclizations

The selective, metal-free generation of alpha-carbonyl cations from simple internal alkynes was accomplished by the addition of a sulfoxide to a densely substituted vinyl cation. The high reactivity of the alpha-carbonyl cations was found to efficiently induce hydrogen and even carbon shift reactions with unusual selecivities. Complex compounds with highly congested tertiary and all-carbon-substituted quartenary carbon centers can thus be accessed in a single step from simple precursors. Mechanistic analysis strongly supports the intermediacy of the title compounds and provides a simple predictive scheme for the migratory aptitude of different substituents.