Exploration of fundamental and synthetic aspects of the intramolecular 4+3 cycloaddition reaction

In this Account, a summary of our work in the exploration and development of intramolecular 4 + 3 cycloaddition reactions between dienes and allylic cations is presented. Alkoxyallylic sulfones are useful precursors for the generation of allylic cations which are good dienophiles. Such substrates allowed a number of important pieces of data concerning the cycloaddition to be obtained. The evolution of the work has involved pursuing other methods for allylic cation generation, an investigation of stereochemical variables and applications, including the total syntheses of aphanamol 1, widdrol, and (+)-dactylol.