Photoredox-Catalysis-Enabled Ring-Opening Functionalization of Aryl Cyclopropanes

Abstract Cyclopropanes have long been recognized as privileged synthons in organic synthesis, providing access to 1,3-difunctionalized scaffolds. However, the synthetic potential of aryl cyclopropanes, one of the most important subclasses of cyclopropanes, is far less explored. Recently, we uncovered a visible-light-promoted strategy for the ring-opening functionalization of a series of aryl cyclopropanes through open-shell intermediates. By leveraging the activation of an aryl radical cation derived from an oxidative single-electron transfer, the C–C bond of the cyclopropane is weakened and cleaves upon a regio- and stereoselective nucleophilic attack with an exogenous nucleophile to provide a benzyl radical that can be readily elaborated to diverse functionalities. 1 Introduction 2 Core Concept of Our Design 3 Photoredox-Catalyzed Oxoamination of Aryl Cyclopropanes 4 Photoredox-Catalyzed Hydroheterofunctionalization of Aryl Cyclopropanes 5 Photoredox-Catalyzed Fluoroallylation of gem-Difluorocyclopropanes 6 Conclusion