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

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 stereo-selective nucleophilic attack with an exogenous nucleophile to provide a benzyl radical that can be readily elaborated to diverse functionalities.1 Introduction2 Core Concept of Our Design3 Photoredox-Catalyzed Oxoamination of Aryl Cyclopropanes4 Photoredox-Catalyzed Hydroheterofunctionalization of Aryl Cy-clopropanes5 Photoredox-Catalyzed Fluoroallylation of gem-Difluorocyclopro-panes6 Conclusion