Zhou Zi-Long, Zhang Yin, Cui Pei-Zhe, Li Jin-Heng
State Key Laboratory Base of Eco-Chemical Engineering, College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China.
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, 730000, China.
Chemistry. 2024 Nov 7;30(62):e202402458. doi: 10.1002/chem.202402458. Epub 2024 Oct 16.
The difunctionalization of alkenes represents a powerful tool to incorporate two functional groups into the alkene bones for increasing molecular complexity and has been widely utilizations in chemical synthesis. Upon the catalysis of the green, sustainable, mild photo-/electrochemistry technologies, much attentions have been attracted to the development of new tactics for the transformations of the important alkene and alkane feedstocks driven by C-H radical functionalization. Herein, we summarize recent advances in the photo-/electrocatalytic difunctionalization of alkenes enabled by C-H radical functionalization. We detailedly discuss the substrate scope and the mechanisms of the photo-/electrocatalytic alkene difunctionalization reactions by selecting impressive synthetic examples, which are divided into four sections based on the final terminated step, including oxidative radical-polar crossover coupling, reductive radical-polar crossover coupling, radical-radical coupling, and transition-metal-catalyzed coupling.
烯烃的双官能团化是一种将两个官能团引入烯烃骨架以增加分子复杂性的强大工具，已在化学合成中得到广泛应用。在绿色、可持续、温和的光/电化学技术催化下，通过C-H自由基官能团化驱动的重要烯烃和烷烃原料转化新策略的开发受到了广泛关注。在此，我们总结了通过C-H自由基官能团化实现的烯烃光/电催化双官能团化的最新进展。我们通过选择令人印象深刻的合成实例，详细讨论了光/电催化烯烃双官能团化反应的底物范围和机理，这些实例根据最终终止步骤分为四个部分，包括氧化自由基-极性交叉偶联、还原自由基-极性交叉偶联、自由基-自由基偶联和过渡金属催化偶联。
