Aryl radical cation promoted remote dioxygenation of cyclopropane derivatives

• DOI: 10.1016/j.xcrp.2022.101233
• Publication Date: 2023-01-18T17:43:54Z
• Authors: Chengkai Pan; Yao Xu; Bin Zhang; Liang Ge; Chi Zhang; Chao Feng
• Keywords: Cyclopropane; Radical ion; SN2 reaction

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