Mechanochemistry has received increasing attention in the past decade. Among which, the mechanochemical C-H bond functionalization has emerged as a hot research topic. In comparison with the traditional solution-based organic reactions, the mechanochemical transformation features solvent-less conditions and short reaction time, constituting a green and efficient synthetic method in the modern chemical society. Notably, given the outstanding features, some long-standing challenges in the

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... solution-based reactions could be well-solved by mechanochemical methods. Therefore, a timely comprehensive overview to recognize the present status of the mechanochemical C-H bond functionalization is of great importance to stimulate the development of more efficient synthetic methods. In this review, the state of the art for mechanochemical C-H bond transformation is presented. The limitation in this research field is also analyzed and the outlook of this area is prospected. Keywords mechanochemistry; C-H bond functionalization; ball milling; solvent-free; green chemistry 机械力化学(mechanochemistry)又称机械化学, 最 早 由 Ostwald 于 1891 年 在 《 Textbook Of General Chemistry》一书中提出 [1] . 第一个机械化学例子是奥地 利学者 Peters 发现的氮化碘受碰击爆炸实验. 当时大家 普遍认为这是一个碰撞产生热化学过程, 但实验证明即 便使用羽毛拨弄几下也会爆炸, 而在这个过程中产生的 热量完全可以忽略不记, 说明机械能确实能促进化学反 应 [2] . 随后, 在 1962 年法兰克福召开的第一届欧洲粉碎 会议上, Peters 发表了题为《Mechanochemistry》的论文, 把机械化学定为物质受机械力的作用而发生化学变化 或者物理化学变化的现象, 首次全面、系统地阐述机械 化学, 并指出机械化学反应是由机械力诱导的化学反 应 [1] [2] [3] . 研究表明, 被施加机械力的反应物会发生各种形 变导致对称性破坏, 从而破坏其内部电子结构, 使其更 加容易发生化学反应 [2,4] . 国际纯粹与应用化学联合会 (IUPAC)将机械化学确定为"十大改变我们的世界的化 学创新"之一 [4n] .