Photoexcited Nitroarenes as Anaerobic Oxygen Atom Transfer ­Reagents

Abstract

Applications of photoexcited nitroarenes have been underdevelopedin organic synthesis. Since early reports on the direct excitationof nitroaromatics with harsh UV light, these synthetically usefulreagents have not been tamed for use in modern synthetic chemistry.We have developed practical synthetic protocols for the anaerobic oxidationof hydrocarbon substrates using commercially available nitroarenesas photochemically activated oxidants under visible light. Usingthis approach, a wide variety of olefins are anaerobically cleaved totheir corresponding carbonyls, and aliphatic C H bonds are hydroxylatedto give alcohols. The anaerobic reaction conditions enable oxidativelysensitive functional groups to be tolerated and the employment ofvisible light makes this method highly sustainable. Mechanistic studiessupport that the photoexcited nitroarene biradical intermediate is responsiblefor the oxygen atom transfer events.1 Introduction2 Alkene Cleavage Promoted by Photoexcited Nitroarenes3 Photoinduce.