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.