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光化学氢原子转移过程在选择性烷烃官能团化中的复兴与进展

Resurgence and advancement of photochemical hydrogen atom transfer processes in selective alkane functionalizations.

作者信息

Chang Liang, Wang Shun, An Qing, Liu Linxuan, Wang Hexiang, Li Yubo, Feng Kaixuan, Zuo Zhiwei

机构信息

School of Pharmacy, Nanjing University of Chinese Medicine Nanjing 210023 China.

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Shanghai 200032 China

出版信息

Chem Sci. 2023 May 22;14(25):6841-6859. doi: 10.1039/d3sc01118f. eCollection 2023 Jun 28.

Abstract

The selective functionalization of alkanes has long been recognized as a prominent challenge and an arduous task in organic synthesis. Hydrogen atom transfer (HAT) processes enable the direct generation of reactive alkyl radicals from feedstock alkanes and have been successfully employed in industrial applications such as the methane chlorination process, Nevertheless, challenges in the regulation of radical generation and reaction pathways have created substantial obstacles in the development of diversified alkane functionalizations. In recent years, the application of photoredox catalysis has provided exciting opportunities for alkane C-H functionalization under extremely mild conditions to trigger HAT processes and achieve radical-mediated functionalizations in a more selective manner. Considerable efforts have been devoted to building more efficient and cost-effective photocatalytic systems for sustainable transformations. In this perspective, we highlight the recent development of photocatalytic systems and provide our views on current challenges and future opportunities in this field.

摘要

长期以来,烷烃的选择性官能团化一直被认为是有机合成中的一项重大挑战和艰巨任务。氢原子转移(HAT)过程能够直接从原料烷烃生成活性烷基自由基,并已成功应用于工业应用,如甲烷氯化过程。然而,自由基生成和反应途径调控方面的挑战在多样化烷烃官能团化的发展中造成了重大障碍。近年来,光氧化还原催化的应用为在极其温和的条件下实现烷烃C-H官能团化提供了令人兴奋的机会,以触发HAT过程并以更具选择性的方式实现自由基介导的官能团化。人们已经投入了大量努力来构建更高效、更具成本效益的光催化体系以实现可持续转化。从这个角度出发,我们重点介绍了光催化体系的最新进展,并对该领域当前的挑战和未来机遇发表了看法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5973/10306100/99042af13280/d3sc01118f-s1.jpg

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