Cell Reports Physical Science ( IF 7.9 ) Pub Date : 2023-01-18 , DOI: 10.1016/j.xcrp.2022.101233 Chengkai Pan , Yao Xu , Bin Zhang , Liang Ge , Chi Zhang , Chao Feng
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.
中文翻译:
芳基阳离子促进环丙烷衍生物的远程双氧化
芳基环丙烷代表了一类有趣的环丙烷,其合成潜力相对未开发。在此,我们提出了一种光氧化还原催化的芳基环丙烷的远程双官能化,可以轻松构建结构多样的 1,3/1,5-双氧化产物。酒精或简单的水被用作亲核试剂。该协议演示了通过跨越环丙烷嵌入的 π 共轭系统的分子内电子相互作用发生的芳基自由基阳离子诱导的远程激活。通过将光氧化还原催化与铜 (II) 介导的自由基加工相结合,实现了形式上的自由基-极性交叉流形。此外,该反应具有条件温和、底物适用范围广、官能团耐受性好、区域选择性高等特点。N 2 类开环功能化。