Taming carbon-centered radicals with cobalt Controlled formation of carbene-radical intermediates and catalytic reactivity via ortho-quinodimethanes

The combined work described in this thesis shows that radical-carbenes can be used in selective reactivity when mediated by [Co(TPP)]. If allyl radical intermediates are generated that are in direct conjugation with the already weak Co-C bond ortho-quinodimethanes dissociate from the catalyst. These reactive ortho-quinodimethane intermediates react further in a series of unexpected reactions to give stable organic products like dihydronapthalenes, E-aryl dienes and dibenzocyclooctenes. As such, we have developed a novel radical-type methodology for the selective synthesis of these three new classes of compounds. Nearly all of the compounds made by the novel catalytic reactions described in this thesis were never reported before.