Selective Transfer Semihydrogenation of Alkynes with H<sub>2</sub>O (D<sub>2</sub>O) as the H (D) Source over a Pd‐P Cathode

Wu, Yongmeng; Liu, Cuibo; Wang, Changhong; Lu, Siyu; Zhang, Bin

doi:10.1002/ange.202009757

Cited by 24 publications

(12 citation statements)

References 78 publications

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“…Although significant progress has been achieved, current reports are still mainly relying on the expensive noble-metal catalysts (e.g., Pt, Pd, Ru, or their related alloys) [9][10][11][12][13] or complicated metal complexes [14][15][16][17] with gaseous hydrogen (H 2 ) or expensive and/or toxic organic hydrogen sources, causing severe concerns on the cost, safety, and sustainability. To solve these problems, an electrochemical strategy has been recently developed by our group for selective semi-hydrogenation of alkynes over a Pd-P cathode by using H 2 O as the hydrogen source 18 . However, good alkenes selectivity required the accurate control of the applied potential and reaction time.…”

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

et al. 2021

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“…This electrochemical method allows the use of electrons as a green reductant source and can be readily controlled by adjusting external parameters, such as the electrolytes and applied voltages, as well as by materials engineering of the catalyst. This approach has been successfully demonstrated for the reductive deuteration of halides [34][35][36] , alkenes [37,38] , alkynes [39] , unsaturated carboxylic acids [40] and deuterated methylation of nitroarenes, as shown in Figure 2A [41,42] .…”

Section: Introductionmentioning

confidence: 99%

Deuterium labelling by electrochemical splitting of heavy water

Liu¹,

Chen²,

Koh³

et al. 2022

Energy Mater

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Deuterium incorporation is crucial in organic synthesis and has wide applications in the pharmaceutical industry. State-of-the-art H/D isotope exchange and chemical defunctionalization for deuterium incorporation suffer from significant drawbacks, including expensive deuterium sources, low deuteration efficiency and poor selectivity. In this perspective, we highlight an alternative pathway for forming C-D bonds by electrocatalytic heavy water splitting (D2O) under mild conditions. In addition, the intrinsic mechanism and examples of the synthesis of deuterated pharmaceuticals are discussed in detail. Finally, we present the challenges facing this field and provide an overall perspective on future research directions.

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“…One of the vital bottlenecks in paired reactions is the electrode materials’/processes’ selectivity, − which has to be chosen to allow the formation of a product without further undesired side reactions. Typically, paired reactions are classified into four types: convergent, parallel, divergent, and linear paired electrolysis (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Green Chemistry: Electrochemical Organic Transformations via Paired Electrolysis

Sbei

Hardwick

Ahmed

2021

ACS Sustainable Chem. Eng.

118

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Paired electrolysis is highly valuable from the viewpoint of efficiency as well as atom and energy economies. In order to optimize the latter two for chemical reactions, the development of paired electrochemical processes is necessary. When both of the electrodes in an electrochemical cell (divided and undivided) are applied as working electrodes, and both sides of the processes (oxidation and reduction) yield valuable compounds, this ideal electrolysis phenomena is defined as paired electrosynthesis. This paired electrolysis offers the opportunity to reduce the spent energy and time, when compared with a single electrolysis system that is only used to achieve a product of interest, while ignoring the other side of the electrolysis (anodic or cathodic). In an ideal case, 200% current efficiency could be achieved during paired electrosynthesis using cathodic and anodic processes to provide the same product. Paired electrosynthesis is a highly efficient green process and, therefore, is beneficial for preserving resources and minimizing waste. However, while a paired electrosynthesis is beneficial, both oxidation and reduction processes must be compatible to counter the yield losses and equally ease separation and purification of both sides of the electrode products. Greater efforts are required to perform paired electrosynthesis with a more systematic and rational approach to achieve optimal products under paired conditions. Nevertheless, new computational tools could be applied for assistance in this matter. There is a considerable level of adventure in designing new paired electrosynthetic processes and accompanying opportunities to design innovative and powerful synthetic strategies. Herein, an overview of several examples of paired electrosyntheses and their advantages are summarized that will aid researchers to both develop a greater understanding of this subject and subsequently employ paired electrolysis for green and sustainable synthesis of organic molecules.

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Selective Transfer Semihydrogenation of Alkynes with H₂O (D₂O) as the H (D) Source over a Pd‐P Cathode

Cited by 24 publications

References 78 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

Deuterium labelling by electrochemical splitting of heavy water

Green Chemistry: Electrochemical Organic Transformations via Paired Electrolysis

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Selective Transfer Semihydrogenation of Alkynes with H2O (D2O) as the H (D) Source over a Pd‐P Cathode

Cited by 24 publications

References 78 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

Deuterium labelling by electrochemical splitting of heavy water

Green Chemistry: Electrochemical Organic Transformations via Paired Electrolysis

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Product

Resources

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Selective Transfer Semihydrogenation of Alkynes with H₂O (D₂O) as the H (D) Source over a Pd‐P Cathode