Collections > Electronic Theses and Dissertations > Alkene Difunctionalization using Hydroxamic Acids

Alkene difunctionalizations are a core transformation in synthetic organic chemistry. A majority of these reactions proceed through polar or transition-metal-catalyzed methods. Alkene difunctionalizations that pass through a free radical reaction manifold are less common. Even less common are radical-based alkene difunctionalizations utilizing oxygen-centered radicals, which are well known for their high reactivity. Disclosed herein is technology which controls the reactivity of oxygen-centered radicals, allowing them to be used for useful and productive synthetic chemistry. The hydroxamic acid functional group was utilized for this purpose. An intermolecular alkene dioxygenation using molecular oxygen as an O-atom source was developed. Derivatives of the hydroxamic acid functional group, N-hydroxy carbamates, were crucial to the success of the reaction. The ability of hydroxamic acids to function as hydrogen-atom donors capable of reducing carbon-centered radicals to alkanes was also discovered. The use of this property lead to the development of an intramolecular formal alkene hydration and cascade diene carbocyclization reaction.