σ-Alkynyl Adsorption Enables Electrocatalytic Semihydrogenation of Terminal Alkynes with Easy-Reducible/Passivated Groups over Amorphous PdSx Nanocapsules DOI
Huizhi Li, Ying Gao, Yongmeng Wu

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(42), P. 19456 - 19465

Published: Oct. 5, 2022

Highly chemo- and regioselective semihydrogenation of alkynes is significant challenging for the synthesis functionalized alkenes. Here, a sequential self-template method used to synthesize amorphous palladium sulfide nanocapsules (PdSx ANCs), which enables electrocatalytic terminal in H2O with excellent tolerance easily reducible groups (e.g., C–I/Br/Cl, C═O) metal center deactivating skeletons quinolyl, carboxyl, nitrile). Mechanistic studies demonstrate that specific σ-alkynyl adsorption via carbon negligible alkene on isolated Pd2+ sites ensure successful various alkenes outstanding time-irrelevant selectivity wide potential range. The key hydrogen radical intermediates are validated by electron paramagnetic resonance high-resolution mass spectrometry. Gram-scale 4-bromostyrene expedient preparation deuterated precursors drugs D2O show promising applications. Impressively, PdSx ANCs can be applied prevailing thermocatalytic alkyne using H2.

Language: Английский

Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source DOI
Cuibo Liu, Yongmeng Wu, Bo‐Hang Zhao

et al.

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(13), P. 1872 - 1883

Published: June 14, 2023

ConspectusThe hydrogenation reaction is one of the most frequently used transformations in organic synthesis. Electrocatalytic by using water (H2O) as hydrogen source offers an efficient and sustainable approach to synthesize hydrogenated products under ambient conditions. Such a technique can avoid use high-pressure flammable gas or other toxic/expensive donors, which usually cause environmental, safety, cost concerns. Interestingly, utilizing easily available heavy (D2O) for deuterated syntheses also attractive due widespread applications molecules synthesis pharmaceutical industry. Despite impressive achievements, electrode selection mainly relies on trial-and-error modes, how electrodes dictate outcomes remains elusive. Therefore, rational design nanostructured driving electrocatalytic series organics via H2O electrolysis developed.In this Account, we review recent advances different types functional groups, including C≡C, C≡N, C═C, C═O, C-Br/I bonds, -NO2, N-heterocycles, with over cathodes. First, general steps (reactant/intermediate adsorption, active atomic (H*) formation, surface reaction, product desorption) are analyzed, key factors proposed optimize performance (e.g., selectivity, activity, Faradaic efficiency (FE), rate, productivity) inhibit side reactions. Then, ex situ spectroscopic tools study intermediates interpret mechanisms introduced. Third, based knowledge mechanisms, introduce catalyst principles detail adoption reactants intermediates, promote formation H* from electrolysis, evolution reactions, improve FEs, space-time productivity products. We then some typical examples. (i) P- S-modified Pd decrease C═C adsorption enabling semihydrogenation alkynes high selectivity FEs at lower potentials. creating high-curvature nanotips concentrate substrates further speeds up process. (ii) By introducing low-coordination sites into Fe combining fluorine modify Co facilitate nitriles N-heterocycles activity obtained. (iii) forming isolated induce specific σ-alkynyl steering S vacancies Co3S4-x preferentially adsorb reduced group-decorated nitroarenes chemoselectivity realized. (iv) For reactant participated designing hydrophobic diffusion layer-supported ultrasmall Cu nanoparticles enhance mass transfer, activation, H2 ethylene ampere-level production 97.7% FE accomplished. Finally, provide outlook current challenges promising opportunities area. believe that summarized here paradigm highly selective nanomaterials achieve fascinating performances.

Language: Английский

Citations

53
Electrochemical radical-polar crossover: a radical approach to polar chemistry DOI

Zhoumei Tan,

Haonan Zhang, Kun Xu

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(2), P. 450 - 470

Published: Nov. 3, 2023

Language: Английский

Citations

50
Room Temperature Construction of Vicinal Amino Alcohols via Electroreductive Cross-Coupling of N-Heteroarenes and Carbonyls DOI

Maorui Wang,

Chengqian Zhang, Chenggang Ci

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10967 - 10973

Published: April 19, 2023

Despite the widespread applications of α-hydroxyalkyl cyclic amines, direct and diverse access to such a class unique vicinal amino alcohols still remains, date, challenge. Here, through strategy electroreductive α-hydroxyalkylation inactive N-heteroarenes with ketones or electron-rich arylaldehydes, we describe room temperature approach for construction which features broad substrate scope, operational simplicity, high chemoselectivity, no need pressurized H2 gas transition metal catalysts. The zinc ion generated from anode oxidation plays crucial role in activation both reactants by decreasing their reduction potentials. electroreduction combination Lewis acids this work is anticipated develop more useful transformations.

Language: Английский

Citations

46
Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes DOI

Keming Yang,

Tian Feng, Youai Qiu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 12, 2023

Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.

Language: Английский

Citations

43
Deuterodehalogenation Under Net Reductive or Redox‐Neutral Conditions Enabled by Paired Electrolysis DOI Open Access
Devin Wood, Song Lin

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 4, 2023

Interest in deuterated active pharmaceutical ingredients (APIs) is increasing as deuteration holds promise for kinetic isotope effect (KIE) regulated fine-tuning of API performance. Moreover, deuterium labeling frequently carried out to study organic and bioorganic reaction mechanisms facilitate complex target synthesis. As such, methods highly selective molecules are desirable. Herein, we present an electrochemical method the deuterodehalogenation benzylic halides via a radical-polar crossover mechanism, using inexpensive oxide (D

Language: Английский

Citations

41
Electroreduction of unactivated alkenes using water as hydrogen source DOI Creative Commons
Yanwei Wang, Qian Wang, Lei Wu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 30, 2024

Abstract Herein, we report an electroreduction of unactivated alkyl alkenes enabled by [Fe]-H, which is provided through the combination anodic iron salts and silane generated in situ via cathodic reduction, using H 2 O as H-source. The catalytic amounts Si-additive work H-carrier from to generate a highly active species under continuous electrochemical conditions. This approach shows broad substrate scope good functional group compatibility. In addition hydrogenation, use D instead provides desired deuterated products yields with excellent D-incorporation (up >99%). Further late-stage hydrogenation complex molecules drug derivatives demonstrate potential application pharmaceutical industry. Mechanistic studies are performed provide support for proposed mechanistic pathway.

Language: Английский

Citations

21
A hydrogenative oxidation strategy for the single-step synthesis of lactams from N-heteroarenes using water DOI
Yaoyu Liang, Jie Luo, Cai You

et al.

Nature Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 20, 2025

Language: Английский

Citations

2
Electrocatalytic Alkene Hydrogenation/Deuteration DOI

Faxiang Bu,

Yuqi Deng,

Lijun Lu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 4, 2025

Traditional reductions of alkenes, such as using stoichiometric reductants with waste generation and catalytic hydrogenation high-pressure H2, are accompanied by environmental or safety issues. Herein, we demonstrated a universal method for the electrocatalytic deuteration alkenes modified electrodes under ambient temperature. The key M-H/M-D species alkene reduction were generated from electrolysis H2O/D2O on electrodes, which avoided usage H2 D2. Mono-, di-, tri-, tetra-substituted successfully reduced in this system H2O D2O hydrogen deuterium sources. Electron-donating/-withdrawing other easily reducible functional groups, complicated natural products drugs all reductive hydrogenated deuterated excellent yields (85 examples, up to 99%). Faraday efficiency efficient could reach 84%. Moreover, amount metal decrease less than 0.01 mol %.

Language: Английский

Citations

2
Electrochemical Arylation of Aldehydes, Ketones, and Alcohols: from Cathodic Reduction to Convergent Paired Electrolysis DOI
Sheng Zhang, Lijun Li, Jinɡjinɡ Li

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(13), P. 7275 - 7282

Published: Dec. 30, 2020

Abstract Arylation of carbonyls, one the most common approaches toward alcohols, has received tremendous attention, as alcohols are important feedstocks and building blocks in organic synthesis. Despite great progress, there is still a gap to develop an ideal arylation method featuring mild conditions, good functional group tolerance, readily available starting materials. We now show that electrochemical can fill gap. By taking advantage synthetic electrochemistry, commercially aldehydes (ketones) benzylic be arylated provide general scalable access structurally diverse (97 examples, >10 gram‐scale). More importantly, convergent paired electrolysis, but challenging technology, was employed transform low‐value into more useful alcohols. Detailed mechanism study suggests two plausible pathways involved redox neutral α‐arylation

Language: Английский

Citations

122
Direct electrochemical defluorinative carboxylation of α-CF3 alkenes with carbon dioxide DOI Creative Commons
Xiaotong Gao, Zheng Zhang, Xin Wang

et al.

Chemical Science, Journal Year: 2020, Volume and Issue: 11(38), P. 10414 - 10420

Published: Jan. 1, 2020

A γ-carboxylation of α-CF3 alkenes with CO2 using platinum plate as both working cathode and nonsacrificial anode has been developed.

Language: Английский

Citations

115