芳烃的氢芳基化反应通过还原自由基-极性交叉反应实现。
Hydroarylation of Arenes via Reductive Radical-Polar Crossover.
机构信息
Department of Chemistry and Winship Cancer Institute, Emory University, Atlanta, Georgia 30322, United States.
出版信息
J Am Chem Soc. 2020 May 20;142(20):9163-9168. doi: 10.1021/jacs.0c03926. Epub 2020 May 11.
Abstract
A photocatalytic system for the dearomative hydroarylation of benzene derivatives has been developed. Using a combination of an organic photoredox catalyst and an amine reductant, this process operates through a reductive radical-polar crossover mechanism where aryl halide reduction triggers a regioselective radical cyclization event, followed by anion formation and quenching to produce a range of complex spirocyclic cyclohexadienes. This light-driven protocol functions at room temperature in a green solvent system (aq. MeCN) without the need for precious metal-based catalysts or reagents or the generation of stoichiometric metal byproducts.
摘要
已经开发出一种用于苯衍生物去芳构化氢芳基化的光催化体系。该过程采用有机光氧化还原催化剂和胺还原剂的组合，通过还原自由基-极性交叉机制进行，其中芳基卤化物的还原引发区域选择性自由基环化反应，随后形成阴离子并猝灭，生成一系列复杂的螺环环己二烯。该光驱动方案在室温下、在绿色溶剂体系（aq. MeCN）中运行，无需使用基于贵金属的催化剂或试剂，也无需生成等摩尔量的金属副产物。
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