Aryl radical cation promoted remote dioxygenation of cyclopropane derivatives
Chengkai Pan, Yao Xu, Bin Zhang, Liang Ge, Chi Zhang, Chao Feng
Abstract
Aryl cyclopropane represents an interesting class of cyclopropanes with relatively underexplored synthetic potential. Herein, we present a photoredox-catalyzed remote difunctionalization of aryl cyclopropanes, which enables facile construction of structurally diverse 1,3/1,5-dioxygenation products. Either alcohol or simply water is used as a nucleophile. This protocol demonstrates aryl radical cation-induced remote activation occurring via intramolecular electronic interaction spanning a cyclopropane-embedded π-conjugated system. By merging photoredox catalysis with copper(II)-mediated radical elaboration, a formal radical-polar crossover manifold is realized. Moreover, this reaction features mild conditions, a wide substrate scope, good functional group tolerance, and high regioselectivities. Preliminary mechanistic experiments probe the radical-involved process, indicating a concerted SN2-like ring-opening functionalization.