Electro‐Synthesis of Organic Compounds with Heterogeneous Catalysis DOI Creative Commons
Tariq Ali, Haiyan Wang, Waseem Iqbal

et al.

Advanced Science, Journal Year: 2022, Volume and Issue: 10(1)

Published: Nov. 18, 2022

Electro-organic synthesis has attracted a lot of attention in pharmaceutical science, medicinal chemistry, and future industrial applications energy storage conversion. To date, there not been detailed review on electro-organic with the strategy heterogeneous catalysis. In this review, most recent advances synthesizing value-added chemicals by catalysis are summarized. An overview electrocatalytic oxidation reduction processes as well paired electrocatalysis is provided, anodic alcohols (monohydric polyhydric), aldehydes, amines discussed. This also provides in-depth insight into cathodic carboxylates, carbon dioxide, CC, C≡C, reductive coupling reactions. Moreover, electro-synthesis methods, including parallel paired, sequential divergent convergent electrolysis, Additionally, strategies developed to achieve high electrosynthesis efficiency associated challenges addressed. It believed that promising direction organic electrochemistry, offering numerous opportunities develop new reaction methods.

Language: Английский

Electrooxidative palladium- and enantioselective rhodium-catalyzed [3 + 2] spiroannulations DOI Creative Commons
Wen Wei, Alexej Scheremetjew, Lutz Ackermann

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(9), P. 2783 - 2788

Published: Jan. 1, 2022

Despite indisputable progress in the development of electrochemical transformations, electrocatalytic annulations for synthesis biologically relevant three-dimensional spirocyclic compounds has as yet not been accomplished. In sharp contrast, herein, we describe palladaelectro-catalyzed C-H activation/[3 + 2] spiroannulation alkynes by 1-aryl-2-naphthols. Likewise, a cationic rhodium(iii) catalyst was shown to enable electrooxidative [3 spiroannulations via formal C(sp3)-H activations. The versatile featured broad substrate scope, employing electricity green oxidant lieu stoichiometric chemical oxidants under mild conditions. An array enones and diverse spiropyrazolones, bearing all-carbon quaternary stereogenic centers were thereby accessed user-friendly undivided cell setup, with molecular hydrogen sole byproduct.

Language: Английский

Citations

72
Asymmetric-waveform alternating current-promoted silver catalysis for C–H phosphorylation DOI
Li Zeng,

Ying Jiao,

Weishun Yan

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(2), P. 172 - 181

Published: Jan. 5, 2023

Language: Английский

Citations

49
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

46
Transition metal-catalyzed organic reactions in undivided electrochemical cells DOI Creative Commons
Cong Ma, Ping Fang, Dong Liu

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(39), P. 12866 - 12873

Published: Jan. 1, 2021

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts alter selectivity given transformation.

Language: Английский

Citations

85
Green strategies for transition metal-catalyzed C–H activation in molecular syntheses DOI Creative Commons
Uttam Dhawa, Nikolaos Kaplaneris, Lutz Ackermann

et al.

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(17), P. 4886 - 4913

Published: Jan. 1, 2021

Sustainable strategies for the activation of inert C–H bonds towards improved resource-economy.

Language: Английский

Citations

80
Mediator-Enabled Electrocatalysis with Ligandless Copper for Anaerobic Chan–Lam Coupling Reactions DOI

Benjamin R. Walker,

Shuhei Manabe, Andrew T. Brusoe

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(16), P. 6257 - 6265

Published: April 16, 2021

Simple copper salts serve as catalysts to effect C–X bond-forming reactions in some of the most utilized transformations synthesis, including oxidative coupling aryl boronic acids and amines. However, these Chan–Lam have historically relied on chemical oxidants that limit their applicability beyond small-scale synthesis. Despite success replacing strong with electrochemistry for a variety metal-catalyzed processes, electrooxidative ligandless are plagued by slow electron-transfer kinetics, irreversible plating, competitive substrate oxidation. Herein, we report implementation substoichiometric quantities redox mediators address limitations Cu-catalyzed electrosynthesis. Mechanistic studies reveal multiple roles (i) rapidly oxidizing low-valent Cu intermediates, (ii) stripping metal from cathode regenerate catalyst active Pt surface proton reduction, (iii) providing anodic overcharge protection prevent This strategy is applied aryl-, heteroaryl-, alkylamines arylboronic absence oxidants. Couplings under electrochemical conditions occur higher yields shorter reaction times than conventional air provide complementary reactivity.

Language: Английский

Citations

75
Enantioselective palladaelectro-catalyzed C–H olefinations and allylations for N–C axial chirality DOI Creative Commons
Uttam Dhawa, Tomasz Wdowik, Xiaoyan Hou

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(42), P. 14182 - 14188

Published: Jan. 1, 2021

Enantioselective palladaelectro-catalyzed C-H alkenylations and allylations were achieved with easily-accessible amino acids as transient directing groups. This strategy provided access to highly enantiomerically-enriched N-C axially chiral scaffolds under exceedingly mild conditions. The synthetic utility of our was demonstrated by a variety alkenes, while the versatility approach reflected atroposelective allylations. Computational studies insights into facile activation seven-membered palladacycle.

Language: Английский

Citations

75
Electrooxidative Rhodium‐Catalyzed [5+2] Annulations via C−H/O−H Activations DOI Creative Commons
Yulei Wang, João C. A. Oliveira, Zhipeng Lin

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(12), P. 6419 - 6424

Published: Jan. 20, 2021

Abstract Electrooxidative annulations involving mild transition metal‐catalyzed C−H activation have emerged as a transformative strategy for the rapid construction of five‐ and six‐membered heterocycles. In contrast, we herein describe first electrochemical [5+2] cycloadditions to assemble valuable seven‐membered benzoxepine skeletons by C−H/O−H activation. The efficient alkyne annulation featured ample substrate scope, using electricity only oxidant. Mechanistic studies provided strong support rhodium(III/I) regime, benzoxepine‐coordinated rhodium(I) sandwich complex catalyst resting state, which was re‐oxidized rhodium(III) anodic oxidation.

Language: Английский

Citations

74
Reaching the Full Potential of Electroorganic Synthesis by Paired Electrolysis DOI
Wenzhao Zhang,

Nianmin Hong,

Song Lu

et al.

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(9), P. 2574 - 2584

Published: April 9, 2021

Abstract Electroorganic synthesis has recently become a rapidly blossoming research area within the organic community. It should be noted that electrochemical reaction is always balanced system with two half‐cell reactions‐oxidation and reduction. Most strategies, however, typically focus on one of sides for desired transformations. Paired electrolysis desirable half reactions running simultaneously, thus maximizing overall margin atom energy economy. Meanwhile, spatial separation between oxidation reduction essential feature electrochemistry, offering unique opportunities development redox‐neutral would otherwise challenging to accomplish in conventional flask setting. This review discusses most recent illustrative examples paired special emphasis sequential convergent processes.

Language: Английский

Citations

65
Electrocatalytic Allylic C−H Alkylation Enabled by a Dual‐Function Cobalt Catalyst** DOI
Ming Chen,

Zheng‐Jian Wu,

Jinshuai Song

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(14)

Published: Feb. 7, 2022

The direct functionalization of allylic C-H bonds with nucleophiles minimizes pre-functionalization and converts inexpensive, abundantly available materials to value-added alkenyl-substituted products but remains challenging. Here we report an electrocatalytic alkylation reaction carbon employing easily cobalt-salen complex as the molecular catalyst. These C(sp3 )-H/C(sp3 )-H cross-coupling reactions proceed through H2 evolution require no external chemical oxidants. Importantly, mild conditions unique radical process ensure excellent functional group tolerance substrate compatibility both linear branched terminal alkenes. synthetic utility electrochemical method is highlighted by its scalability (up 200 mmol scale) under low loading electrolyte (down 0.05 equiv) successful application in late-stage structures.

Language: Английский

Citations

64