Synthesis of diquinanes and triquinanes via fragmentation chemistry of deltacyclanes

This thesis describes research carried out with the goal of developing synthetically useful chemistry from metal-catalyzed (2+2+2) homo Diels-Alder cycloadditions. Deltacyclane cycloadducts obtained from the Ni(0)-catalyzed homo Diels-Alder reaction of tert-butoxy norbornadiene and electron-deficient olefins are fragmented to diquinane and triquinane skeleta.;Improvements in the oxymercuration of the cyclopropane moiety of deltacyclane cycloadducts, particularly hydroxymercuration, has led to efficient routes to mercury-substituted brendanols and brendanones. Reduction or functionalization of the organomercurial functionality provided demercurated brendanols and brendanones. Investigation of Baeyer-Villiger and alkoxy radical fragmentation of brendanones and brendanols respectively (with and without mercury substituents) has led to rapid, selective syntheses of functionalized diquinanes and triquinanes.