Electrochemical oxidative aminocarbonylation of terminal alkynes

Zeng, Li; Li, Haoran; Hu, Jingcheng; Zhang, Dongchao; Hu, Jianlong; Peng, Pan; Wang, Shengchun; Shi, Renyi; Peng, Jiaqi; Pao, Chih‐Wen; Chen, Jeng-Lung; Lee, Jyh‐Fu; Zhang, Heng; Chen, Yi‐Hung; Lei, Aiwen

doi:10.1038/s41929-020-0443-z

Cited by 96 publications

(45 citation statements)

References 42 publications

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“…Electrochemistry has provided an efficient and sustainable platform for synthesizing value-added fine chemicals [21][22][23][24][25][26] . Cubased catalysts are widely used in many electrochemical reactions due to their abundance, robustness, and superior catalytic activity [27][28][29][30][31][32][33][34] .…”

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confidence: 99%

Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water

et al. 2021

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Electrocatalytic alkyne semi-hydrogenation to alkenes with water as the hydrogen source using a low-cost noble-metal-free catalyst is highly desirable but challenging because of their over-hydrogenation to undesired alkanes. Here, we propose that an ideal catalyst should have the appropriate binding energy with active atomic hydrogen (H*) from water electrolysis and a weaker adsorption with an alkene, thus promoting alkyne semi-hydrogenation and avoiding over-hydrogenation. So, surface sulfur-doped and -adsorbed low-coordinated copper nanowire sponges are designedly synthesized via in situ electroreduction of copper sulfide and enable electrocatalytic alkyne semi-hydrogenation with over 99% selectivity using water as the hydrogen source, outperforming a copper counterpart without surface sulfur. Sulfur anion-hydrated cation (S2−-K+(H2O)n) networks between the surface adsorbed S2− and K+ in the KOH electrolyte boost the production of active H* from water electrolysis. And the trace doping of sulfur weakens the alkene adsorption, avoiding over-hydrogenation. Our catalyst also shows wide substrate scopes, up to 99% alkenes selectivity, good reducible groups compatibility, and easily synthesized deuterated alkenes, highlighting the promising potential of this method.

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confidence: 99%

Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water

et al. 2021

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“…Moreover, the discovery of new reactivities enabled by electrochemistry promotes further adoption of this technique [6] . A number of exciting electrochemical methodologies have recently been discovered, achieving transformations that would be, otherwise, either challenging or even impossible with conventional techniques [7–12] …”

Section: Figurementioning

confidence: 99%

“…[6] A number of exciting electrochemical methodologies have recently been discovered, achieving transformations that would be, otherwise, either challenging or even impossible with conventional techniques. [7][8][9][10][11][12] Nevertheless, electrochemical synthesis is still considered as a niche technique with high entry barriers, [4,6,13] such as the relative low experimentation throughput, attributed to the complex electrochemistry setup, limiting the ability to quickly identify and optimize new chemistries. Both academic groups and commercial companies have devoted to developing electrochemistry-friendly screening methodologies and standardized equipment to streamline the adoption of electroorganic synthesis.…”

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confidence: 99%

A Multifunctional Microfluidic Platform for High‐Throughput Experimentation of Electroorganic Chemistry

Rughoobur

Nambiar

et al. 2020

Angewandte Chemie

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Electroorganic synthesis is a promising tool to design sustainable transformations and discover new reactivities. However, the added setup complexity caused by electrodes in the system impedes efficient screening of reaction conditions. Herein, we present a microfluidic platform that enables automated high‐throughput experimentation (HTE) for electroorganic synthesis at a 15‐microliter scale. Two HTE modules are demonstrated: 1) the rapid electrochemical reaction condition screening for a radical–radical cross‐coupling reaction on micro‐fabricated interdigitated electrodes, and 2) measurements of kinetics for mediated anodic oxidations using the microliter‐scale cyclic voltammetry. The presented modular approach could be deployed for a range of other electroorganic chemistry applications beyond the demonstrated functionalities.

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“…The recent development of SET oxidation or reduction strategy provides an efficient means for molecule activation in a mild and predictable manner (Prier et al, 2013;Chen et al, 2016aChen et al, , 2016bYi et al, 2017). Not surprisingly, visible-light photocatalysis (Perry et al, 2018;Skubi et al, 2016;Chen et al, 2016aChen et al, , 2016bRomero and Nicewicz, 2016;Karkas et al, 2016) and electrocatalysis (Yan et al, 2017;Zhao et al, 2017;Jiang et al, 2018;Jiao et al, 2020;Zeng et al, 2020;Leech and Lam, 2020) represent two ideal protocols for radical reaction invention because of their green and sustainable properties. In addition, some SET oxidants are also been used for the generation of radical species.…”

Section: Introductionmentioning

confidence: 99%

Single Electron Activation of Aryl Carboxylic Acids

Liu

Hou

et al. 2020

iScience

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Aryl carboxylic acids are stable and readily available in great structural diversity both from natural and well-established synthetic procedures, which make them promising starting materials in organic synthesis. The conversion of benzoic acids into high-value molecules is of great importance and have gained much interest of synthetic chemists. The recent development of single-electron (1e À ) activation strategy has been esteemed as a complementary method for the transformation of benzoic acids. In this context, carboxylate groups can be selectively transferred into reactive aryl carboxylic radical, aryl radical, and acyl radical by electrocatalysis, photocatalysis, or in the presence of some SET oxidants. Based on these radical species, remarkable advancements have been achieved for the rapid formation of various chemical bonds over the past 10 years. In this review, we summarize recent advances in single electron activation of aryl carboxylic acids, with an emphasis on reaction scope, catalytic system, limitation, and underlying reaction mechanism.

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Electrochemical oxidative aminocarbonylation of terminal alkynes

Cited by 96 publications

References 42 publications

Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water

Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water

A Multifunctional Microfluidic Platform for High‐Throughput Experimentation of Electroorganic Chemistry

Single Electron Activation of Aryl Carboxylic Acids

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