Recent Progress in Electrochemical Conversion from Biomass Derivatives into High‐Value‐Added Chemicals DOI Creative Commons

Yao Sun,

Jiaming Miao, Xinyi Fan

et al.

Small Structures, Journal Year: 2024, Volume and Issue: 5(7)

Published: April 17, 2024

Selective and efficient electrochemical conversion of cheap abundant biomass derivatives into high‐value‐added products can provide a way to store large‐scale renewable intermittent energy such as wind energy, solar etc. Although large amount research is devoted developing highly catalysts or disclosing the reaction processes, there are always challenges rate selectivity, relevant comprehensive in‐depth discussion relatively scarce. This review introduces basic principles processes from charge transfer pathway conversion. Then, for design anode, representative work summarized discussed in detail point view material adjustment, theoretical calculations, situ characterizations. Finally, insights further optimization systems put forward. It believed that this provides guidance selection, design, application materials organic synthesis.

Language: Английский

Metal‐Free Electrochemical Carboxylation of Organic Halides in the Presence of Catalytic Amounts of an Organomediator DOI
Yanwei Wang, Zhiwei Zhao, Deng Pan

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: Aug. 26, 2022

Herein, an electroreductive carboxylation of organic carbon-halogen bonds (X=Br and Cl) promoted by catalytic amounts naphthalene as mediator is reported. This transformation proceeds smoothly under mild conditions with a broad substrate scope 59 examples, affording the valuable versatile carboxylic acids in moderate to excellent yields without need costly transition metal, wasted stoichiometric metal reductants, or sacrificial anodes. Further late-stage carboxylations natural product drug derivatives demonstrate its synthetic utility. Mechanistic studies confirmed activation via single-electron transfer key role this reaction.

Language: Английский

Citations

87
Electrocarboxylation of Aryl Epoxides with CO2for the Facile and Selective Synthesis of β‐Hydroxy Acids DOI
Yanwei Wang,

Shunyao Tang,

Guoqing Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: July 30, 2022

Abstract Herein, an efficient and facile approach to valuable β‐hydroxy acid derivatives from readily available aryl epoxides CO 2 with high chemo‐ regioselectivity under mild sustainable electrochemical conditions is described. This showed broad substrate scope good functional‐group compatibility. In addition epoxides, four‐ six‐membered cyclic ethers could all be tolerated in the reaction provide synthetically useful hydroxy acids efficiency. Further late‐stage carboxylation of complex molecules drug demonstrated its potential application pharmaceutical industry. Mechanistic studies disclosed possible pathways.

Language: Английский

Citations

76
Unraveling the Structure and Reactivity Patterns of the Indole Radical Cation in Regioselective Electrochemical Oxidative Annulations DOI
Xing Liu, Dali Yang, Zhao Liu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(5), P. 3175 - 3186

Published: Jan. 27, 2023

Oxidation-induced strategy for inert chemical bond activation through highly active radical cation intermediate has exhibited unique reactivity. Understanding the structure and reactivity patterns of intermediates is crucial in mechanistic study will be beneficial developing new reactions. In this work, properties indole cations have been revealed using time-resolved transient absorption spectroscopy, situ electrochemical UV–vis, electron paramagnetic resonance (EPR) technique. Density functional theory (DFT) calculations were used to explain predict regioselectivity several oxidative annulations. Based on understanding inherent cations, two different regioselective annulations indoles successfully developed under oxidation conditions. Varieties furo[2,3-b]indolines furo[3,2-b]indolines synthesized good yields with high regioselectivities. Our insights into promote further development oxidation-induced functionalizations.

Language: Английский

Citations

64
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

48
Electrochemically Driven Hydrogen Atom Transfer Catalysis: A Tool for C(sp3)/Si–H Functionalization and Hydrofunctionalization of Alkenes DOI Creative Commons
Sheng Zhang, Michael Findlater

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8731 - 8751

Published: June 16, 2023

Electrochemically driven hydrogen atom transfer (HAT) catalysis provides a complementary approach for the transformation of redox-inactive substrates that would be inaccessible to conventional electron (ET) catalysis. Moreover, electrochemically HAT could promote organic transformations with either abstraction or donation as key step. It versatile and effective tool direct functionalization C(sp3)–H/Si–H bonds hydrofunctionalization alkenes. Despite these attractive properties, has been largely overlooked due lack understanding both catalytic mechanism how catalyst selection should occur. In this Review, we give an overview applications in The mechanistic pathways, physical properties mediators, state-of-the-art examples are described discussed.

Language: Английский

Citations

47
Paired Oxidative and Reductive Catalysis: Breaking the Potential Barrier of Electrochemical C(sp3)−H Alkenylation** DOI

Long Zou,

Xiaofan Wang,

Siqi Xiang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 1, 2023

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required enable their C(sp3 )-H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating catalysis with reductive in one cell without interference, which earth-abundant iron and nickel employed as anodic cathodic catalysts, respectively. This approach lowers previously high oxidation potential for alkane activation, enabling electrochemical functionalization at ultra-low ≈0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

Language: Английский

Citations

46
Programmed alternating current optimization of Cu-catalyzed C-H bond transformations DOI
Li Zeng, Qinghong Yang, Jianxing Wang

et al.

Science, Journal Year: 2024, Volume and Issue: 385(6705), P. 216 - 223

Published: July 11, 2024

Direct current (DC) electrosynthesis, which has undergone optimization over the past century, plays a pivotal role in variety of industrial processes. Alternating (AC) characterized by polarity reversal and periodic fluctuations, may be advantageous for multiple chemical reactions, but apparatus, principles, application scenarios remain underdeveloped. In this work, we introduce protocol programmed AC (pAC) electrosynthesis that systematically adjusts currents, frequencies, duty ratios. The representative pAC waveforms facilitates copper-catalyzed carbon-hydrogen bond cleavage cross-coupling difunctionalization reactions exhibit suboptimal performance under DC oxidation conditions. Moreover, observing catalyst dynamic variation diverse waveform applications provides mechanistic insight.

Language: Английский

Citations

29
Organophotoelectrocatalytic C(sp2)–H alkylation of heteroarenes with unactivated C(sp3)–H compounds DOI

Qinhui Wan,

Xia-Die Wu,

Zhong-Wei Hou

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(42), P. 5502 - 5505

Published: Jan. 1, 2024

An organophotoelectrocatalytic method for the C(sp 2 )–H alkylation of heteroarenes with unactivated 3 compounds via dehydrogenation cross-coupling was developed.

Language: Английский

Citations

28
Photoelectrochemically driven iron-catalysed C(sp3)−H borylation of alkanes DOI

Yangmin Cao,

Cheng Huang, Qingquan Lu

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(4), P. 537 - 544

Published: Jan. 31, 2024

Language: Английский

Citations

23
Operando film-electrochemical EPR spectroscopy tracks radical intermediates in surface-immobilized catalysts DOI Creative Commons
Maryam Seif-Eddine, Samuel J. Cobb, Yunfei Dang

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(6), P. 1015 - 1023

Published: Feb. 14, 2024

The development of surface-immobilized molecular redox catalysts is an emerging research field with promising applications in sustainable chemistry. In electrocatalysis, paramagnetic species are often key intermediates the mechanistic cycle but inherently difficult to detect and follow by conventional situ techniques. We report a new method, operando film-electrochemical electron resonance spectroscopy (FE-EPR), which enables studies electrocatalysts. This technique radicals formed during reactions be followed real time under flow conditions, at room temperature aqueous solution. Detailed insight into catalysts, as exemplified here through alcohol oxidation catalysis nitroxide, possible detecting active-site sensitively quantitatively operando, thereby enabling resolution reaction kinetics. Our finding that surface electron-transfer rate, same order magnitude rate (accessible from FE-EPR), limits catalytic efficiency has implications for future design better catalysts.

Language: Английский

Citations

17