Redox Inversion: A Radical Analogue of Umpolung Reactivity for Base- and Metal-Free Catalytic C(sp 3 )–C(sp 3 ) Coupling
Redox Inversion: A Radical Analogue of Umpolung Reactivity for Base- and Metal-Free Catalytic C(sp 3 )–C(sp 3 ) Coupling
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氧化还原反转：无碱和无金属催化 C(sp 3 )→C(sp 3 ) 偶联的 Umpolung 反应性的根本模拟
DOI：
10.1021/acs.joc.2c02877
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Roberts, Courtney C.
中科院分区：
文献类型：
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作者：
Seong, Chris M.;Ansel, Annabel Q.;Roberts, Courtney C.
烷基-烷基键的构造是有机合成的有力工具。氧化还原反转，定义为将官能团的供体/受体结构转换为其受体/供体结构，用于C(sp3) -C （sp3）耦合。我们报道了羧酸通过自由基-自由基偶联形成联苯的光催化偶联。机械洞察力是通过控制反应获得的。羧酸和它的氧化还原活性酯之间的这种未探索的氧化还原-反关系在催化中实现。
The construction of alkyl–alkyl bonds is a powerful tool in organic synthesis. Redox inversion, defined as switching the donor/acceptor profile of a functional group to its acceptor/donor profile, is used for C(sp3)–C(sp3) coupling. We report a photocatalytic coupling of carboxylic acids to form bibenzyls through a radical–radical coupling. Mechanistic insight is gained through control reactions. This unexplored redox-opposite relationship between a carboxylic acid and its redox-active ester is implemented in catalysis.