Wang Xinghua, He Jing, Wang Ya-Nan, Zhao Zhenyan, Jiang Kui, Yang Wei, Zhang Tao, Jia Shiqi, Zhong Kangbao, Niu Linbin, Lan Yu
College of Chemistry, and Pingyuan Laboratory, Zhengzhou University, Zhengzhou, Henan 450001, P. R. China.
School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Chemical Theory and Mechanism, Chongqing University, Chongqing 401331, P. R. China.
Chem Rev. 2024 Sep 11;124(17):10192-10280. doi: 10.1021/acs.chemrev.4c00188. Epub 2024 Aug 8.
Radical C-H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) are Earth-abundant and can be employed to regulate radical C-H functionalization. The use of such metals is desirable because of the diverse interaction modes between first-row transition metal complexes and radical species including radical addition to the metal center, radical addition to the ligand of metal complexes, radical substitution of the metal complexes, single-electron transfer between radicals and metal complexes, hydrogen atom transfer between radicals and metal complexes, and noncovalent interaction between the radicals and metal complexes. Such interactions could improve the reactivity, diversity, and selectivity of radical transformations to allow for more challenging radical C-H functionalization reactions. This review examines the achievements in this promising area over the past decade, with a focus on the state-of-the-art while also discussing existing limitations and the enormous potential of high-value radical C-H functionalization regulated by these metals. The aim is to provide the reader with a detailed account of the strategies and mechanisms associated with such functionalization.
自由基C-H官能团化是一种有用的方法，可通过避免底物预活化并以较少步骤获得目标分子来简化合成路线。第一行过渡金属（钛、钒、铬、锰、铁、钴、镍和铜）储量丰富，可用于调控自由基C-H官能团化。使用这些金属是可取的，因为第一行过渡金属配合物与自由基物种之间存在多种相互作用模式，包括自由基加成到金属中心、自由基加成到金属配合物的配体、金属配合物的自由基取代、自由基与金属配合物之间的单电子转移、自由基与金属配合物之间的氢原子转移以及自由基与金属配合物之间的非共价相互作用。这些相互作用可以提高自由基转化的反应性、多样性和选择性，从而实现更具挑战性的自由基C-H官能团化反应。本文综述了过去十年在这一有前景的领域所取得的成就，重点关注了当前的技术水平，同时也讨论了现有局限性以及这些金属调控的高价值自由基C-H官能团化的巨大潜力。目的是为读者详细介绍与这种官能团化相关的策略和机制。
