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用于单电子转移氧化还原中性反应的微流控电化学。

Microfluidic electrochemistry for single-electron transfer redox-neutral reactions.

机构信息

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.

出版信息

Science. 2020 Jun 19;368(6497):1352-1357. doi: 10.1126/science.aba3823.

DOI:10.1126/science.aba3823
PMID:32554592
Abstract

Electrochemistry offers opportunities to promote single-electron transfer (SET) redox-neutral chemistries similar to those recently discovered using visible-light photocatalysis but without the use of an expensive photocatalyst. Herein, we introduce a microfluidic redox-neutral electrochemistry (μRN-eChem) platform that has broad applicability to SET chemistry, including radical-radical cross-coupling, Minisci-type reactions, and nickel-catalyzed C(sp)-O cross-coupling. The cathode and anode simultaneously generate the corresponding reactive intermediates, and selective transformation is facilitated by the rapid molecular diffusion across a microfluidic channel that outpaces the decomposition of the intermediates. μRN-eChem was shown to enable a two-step gram-scale electrosynthesis of a nematic liquid crystal compound, demonstrating its practicality.

摘要

电化学提供了促进类似于最近使用可见光光催化发现的单电子转移(SET)氧化还原中性化学的机会,但无需使用昂贵的光催化剂。在此,我们引入了一种微流控氧化还原中性电化学(μRN-eChem)平台,该平台具有广泛的适用性,适用于 SET 化学,包括自由基-自由基交叉偶联、Minisci 型反应和镍催化的 C(sp)-O 交叉偶联。阴极和阳极同时生成相应的反应性中间体,并且快速分子扩散通过微流道进行,超过了中间体的分解速度,从而促进了选择性转化。μRN-eChem 被证明能够实现两步克规模的向列液晶化合物的电合成,展示了其实用性。

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