Palladium-Catalyzed Intermolecular Functionalization of Unactivated Methylene C(sp^(3))—H Bonds  

钯催化惰性亚甲基C(sp^(3))—H键分子间官能团化反应(英文)

作　　者：Mingshun Mei Yanghui Zhang 梅明顺;张扬会(同济大学化学科学与工程学院,上海200092;同济大学上海市化学品分析、风险评估与控制重点实验室,上海200092)

机构地区：[1]School of Chemical Science and Engineering,Tongji University,Shanghai 200092 [2]Shanghai Key Laboratory of Chemical Assessment and Sustainability,Tongji University,Shanghai 200092

出　　处：《有机化学》2025年第2期620-640,共21页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(22371211);上海市自然科学基金(23ZR1468700)。

摘　　要：Although transition metal-catalyzed methylene C(sp^(3))—H functionalization is a great challenge, it has made noticeable progress in recent years. This review specifically describes Pd-catalyzed intermolecular functionalization of unactivated methylene C(sp^(3))—H bonds. A variety of reactions, including arylation, alkylation, alkenylation/alkynylation, acetoxylation, amination, halogenation, borylation, and silylation reactions, have been discussed. Due to the inert properties, methylene C(sp^(3))—H functionalization reaction usually relies on the use of directing group strategies, which can not only control regioselectivity but also address low reactivity issue. Various directing groups, including strongly coordinating bidentate auxiliaries and weakly coordinating innate functional groups, have proven to be effective for enabling methylene C(sp^(3))—H functionalization.尽管过渡金属催化的亚甲基C(sp^(3))—H官能团化是一项巨大的挑战,但近年来已取得一系列显著进展.此文综述了钯催化的惰性亚甲基C(sp^(3))—H键的分子间官能化反应,讨论了包括芳基化、烷基化、烯基化/炔基化、乙酰氧基化、胺化、卤化、硼化和硅化在内的多种反应.由于亚甲基C(sp^(3))—H键的惰性特性,其官能化反应通常依赖于导向基策略,这不仅能控制区域选择性,还能解决低反应性问题.各种导向基,包括强配位的双齿辅助基和弱配位的天然官能团,已被证明在实现亚甲基C(sp^(3))—H官能化方面是有效的.

关 键 词：palladium catalysis C-H activation methylene C(sp^(3))-H activation CROSS-COUPLING 

分 类 号：O621.3[理学—有机化学]