Synthetic Organic Electrochemistry: Calling All Engineers.
Synthetic Organic Electrochemistry: Calling All Engineers.
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DOI：
10.1002/anie.201707584
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发表时间：
2018-04-09
期刊：
影响因子：
--
通讯作者：
Baran PS
中科院分区：
文献类型：
--
作者：
Yan M;Kawamata Y;Baran PS
对于许多化学专业的学生来说，电合成（通过利用电动势添加/去除电子来制备材料）几乎等同于生产大宗化学品，例如铝和百万吨级的烧碱（图 1A）。事实上，教科书中经常包含巨型植物的图片来说明电解的概念。 [1]电化学在分析化学中也发挥着重要作用，其中分析物的电解反应低至皮克级，可以定量测定其浓度。 [2]为此目的设计了微型化和基于芯片的传感器。因此，电化学过程在大（百万吨）和小（皮克）尺度上都具有极高的保真度。相反，在这两个极端之间，电化学技术从来都不是实验室规模的合成有机化学家的常规工具（图 1A）。这种尺度（1 mg–1 kg）涵盖了我们化学空间的大部分，涵盖放射化学、药物化学、天然产物合成、合成方法开发、聚合物合成和制药工艺开发，每天都会产生各种不同且日益复杂的分子。具有讽刺意味的是，这种被忽视的尺度体系恰恰是合成有机电化学最初蓬勃发展的地方。 [3, 4] 事实上，探索早在 19 世纪初期就已开始，当时迈克尔·法拉第 (Michael Faraday) 进行了乙酸的电解（图 1B）。 [5]该领域丰富的历史充满了有趣且有益的发现。古老的 Kolbe 电解 (1847) 代表了最早的 CC 键形成反应之一；[6] 塔菲尔重排提供了获取各种碳氢化合物的强大手段。 [7]在 20 世纪 40 年代和 1960 年代之间，西蒙斯氟化反应 [8] 和孟山都己二腈工艺 [9] 凸显了电解以可扩展的方式完成具有挑战性的化学转化的固有能力。电生酸/碱[10, 11]和手性电极[12]在20世纪70年代和80年代的应用代表了有机化学值得重新审视的新前景。介体的发明改善了与电极表面异质电子转移相关的问题，包括动力学势垒和电极钝化。 [13]早在 1900 年代就开始探索使用铬配合物促进醌的电合成。 [14] 20 世纪 60 年代至 80 年代的努力导致了多功能三芳胺 [15] 和硝酰基介体的普及。 [16]的概念
To many students of chemistry, electrosynthesis (the preparation of materials via addition/removal of electrons with the electromotive force) is almost synonymous with the production of bulk chemicals such as aluminum, and caustic soda on megaton scales (Figure 1A). In fact, pictures of gigantic plants are frequently included in textbooks to illustrate the concept of electrolysis.[1] Electrochemistry has also played prominent roles in analytical chemistry wherein electrolytic reactions of analytes in as low as picogram scales allowed quantitative determination of their concentrations.[2] Miniaturized and chip-based sensors have been devised for this purpose. Thus, electrochemical processes have been engineered with great fidelity on both large (megaton) and small (picogram) scales. Conversely, between these two extreme ends of the spectrum, electrochemical techniques have never been a regular tool in the armamentarium of synthetic organic chemists working on laboratory scales (Figure 1A). Such scales (1 mg–1 kg) encompass the majority of our chemical space, spanning radiochemistry, medicinal chemistry, natural product synthesis, synthetic method development, polymer synthesis, and pharmaceutical process development where collections of diverse and ever-increasingly complex molecules are created daily.It is ironic that this neglected scale regime is precisely where synthetic organic electrochemistry originally flourished.[3, 4] In fact, explorations had begun in the early 19th century when Michael Faraday performed the electrolysis of acetic acid (Figure 1B).[5] The rich history of the field is replete with intriguing and enabling discoveries. The venerable Kolbe electrolysis (1847) represents one of the earliest CC bond forming reactions;[6] the Tafel rearrangement offers a powerful means to access various hydrocarbons.[7] Between the 1940s and the 1960s, the Simons fluorination reaction [8] and the Monsanto adiponitrile process [9] highlight the innate ability of electrolysis to accomplish challenging chemical transformations in scalable fashions. The applications of electrogenerated acids/bases [10, 11] and chiral electrodes [12] in the 1970s and 80s represent new vistas in organic chemistry that are worth revisiting. The invention of mediators ameliorated problems associated with heterogeneous electron transfer at electrode surfaces, including kinetic barriers and electrode passivation.[13] The use of chromium complexes to facilitate the electrosynthesis of quinones was explored in as early as the 1900s.[14] Efforts between the 1960s and 1980s led to the popularization of versatile triarylamine [15] and nitroxyl mediators.[16] The concept of
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影响因子：
3.4
作者：
Guetz, Christoph;Baenziger, Markus;Waldvogel, Siegfried R.
通讯作者：
Waldvogel, Siegfried R.
影响因子：
1.6
作者：
Heyrovsky, J
通讯作者：
Heyrovsky, J
影响因子：
18.2
作者：
Horn EJ;Rosen BR;Baran PS
通讯作者：
Baran PS
影响因子：
--
作者：
Hickling, A
通讯作者：
Hickling, A
影响因子：
15
作者：
HUDSON, CM;MARZABADI, MR;NEW, DG
通讯作者：
NEW, DG