Mechanochemical Solvent‐Free Catalytic C−H Methylation

Ni, Shengjun; Hribersek, Matic; Baddigam, Swarna Kumari; Ingner, Fredric J. L.; Orthaber, Andreas; Gates, Paul J.; Pilarski, Lukasz T.

doi:10.1002/anie.202010202

Cited by 86 publications

(39 citation statements)

References 161 publications

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“…An additional energetic aspect of ball milling reactions is that many of them not only proceed without external heating, but some mechanochemical reactions yield the corresponding products in shorter reaction times than solution‐based protocols as previously demonstrated for the mechanosynthesis of MOFs using metal oxides as precursors (Scheme 2), [44,45] or in recent examples of organo‐ and metal‐catalyzed mechanochemical reactions, [124,125] organometallic complex formation, [126] and synthesis of carbon materials [127] . Along these lines, a recent mechanochemical protocol to access nanocrystalline corundum (α‐Al 2 O 3 ) from boehmite [γ‐AlO(OH)] further highlights this aspect [128] .…”

Section: Mechanochemistry and The Twelve Principles Of Green Chemistrymentioning

confidence: 99%

Sustainability Assessment of Mechanochemistry by Using the Twelve Principles of Green Chemistry

2021

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In recent years, mechanochemistry has been growing into a widely accepted alternative for chemical synthesis. In addition to their efficiency and practicality, mechanochemical reactions are also recognized for their sustainability. The association between mechanochemistry and Green Chemistry often originates from the solvent-free nature of most mechanochemical protocols, which can reduce waste production. However, mechanochemistry satisfies more than one of the Principles of Green Chemistry. In this Review we will present a series of examples that will clearly illustrate how mechanochemistry can significantly contribute to the fulfillment of Green Chemistry in a more holistic manner.

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Section: Mechanochemistry and The Twelve Principles Of Green Chemistrymentioning

confidence: 99%

Sustainability Assessment of Mechanochemistry by Using the Twelve Principles of Green Chemistry

2021

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“…甲基在药物中具有"神奇甲基效应", 可以显著调节分子的生物和物理性质 [30][31] . Pilarski 等 [32] 在 2020 年报道了机械力促进的 C-H 键活化甲基化反应(Scheme 15). 作者利用机械化学球磨技术, 以甲基硼酸或者甲基三氟硼酸钾为甲基源, 金属铑为催化剂, 碳酸银为氧化剂, 在球磨中反应 1/3 至 4 h 即可得到目标产物.…”

Section: 机械力促进过渡金属催化的芳基化反应unclassified

Recent Advances in C—H Bond Functionalization under Mechanochemical Conditions

Zhou¹,

Mao²,

Wu³

et al. 2021

Chinese Journal of Organic Chemistry

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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 previous 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] .

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“…64 An exciting recent development disclosed by Pilarski in 2020, was the ability to perform this Rh-catalysed transformation using mechanochemistry (Scheme 16). 65 The ball-milling approach 66 was not only solvent-free, but also highly regioselective. Interestingly, they developed a frequency-dependent regioselective C-H methylation protocol on an indoline substrate (C7 vs. C2 insertion), and explicitly highlighted the advantages of using this ball-milling approach in the preparation of rhodacycles.…”

Section: Introductionmentioning

confidence: 99%