Convergent Paired Electrolysis for [3+2] Cycloaddition of Azidotrimethylsilane with N‐Heterocycles DOI

Abhijit Bankura,

Subhadeep Ghosh, Sumit Biswas

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: 17(21)

Published: May 27, 2024

Abstract A widely used method to obtain tetrazoles is through the azide and nitrile [3+2] cycloaddition. However, this process often involves using non‐recyclable transition metals or Lewis acid catalysts stoichiometric amounts of oxidants additives, which reduces atom efficiency. We have discovered a convergent paired electrochemical reaction perform cycloaddition reaction, without need for metal oxidants. This tetrazolation strategy uses azidotrimethylsilane (TMSN 3 ) N ‐heterocycles in an undivided cell at constant current. use mixture CH CN equivalent H 2 O as co‐solvent room temperature. It crucial produce amount active hydroxyl ions cathodic reduction water. Cyclic voltammetry (CV) studies control experiments confirm that specific electrode electron transfer process, eliminating mediator shuttle electrons. metal‐ oxidant‐free highly compatible with different functional groups produces products moderate good yields. successfully tetrazolated bioactive compounds late stage, scaled up batches efficiently, synthesized free amino‐containing via denitrogenation tetrazoles.

Language: Английский

Recent Advances in Multicomponent Electro‐Organic (Electrochemical) Synthesis of Heterocycles DOI Creative Commons

Sahar Imeni,

Ata Makarem, Ramin Javahershenas

et al.

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(8)

Published: July 20, 2023

Abstract In terms of pharmaceuticals and biological applications, synthesis complex organic molecules is a significant fast‐developing area. this context, electrosynthesis an alternative way to the traditional methods for chemo‐, regio‐, stereoselective syntheses. Electro‐organic reactions occur at room temperature normal pressure, through transferring electrons. It has been found that mild approach preparing electrophilic substrates, bases, nucleophiles in situ , from highly stable low‐level reagents; which can be further applied make heterocycles more accessible. While several promising exist, multi‐component (MCRs) have drawn much attention both academia industry worldwide, since they are cost‐efficient environmentally friendly. Combining MCRs produced great strategy field research. This review focuses on recent advances electrochemical heterocyclic compounds via reactions, reported between 2015 March 2023.

Language: Английский

Citations

34
Electrochemical Difunctionalization of Alkenes DOI

Jing‐Hao Qin,

Jin‐Heng Li,

Ning Nan

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 55(18), P. 2843 - 2859

Published: Feb. 15, 2023

Abstract The electrochemical alkene difunctionalization reaction has become a powerful and sustainable tool for the efficient construction of vicinal difunctionalized structures in organic synthesis. Since only electrons are used as redox agents, avoids need additional catalysts, metal or chemical oxidants does not generate waste. Herein we summarize latest contributions alkenes over last 3–4 years. We discuss detail features, scope, limitations, mechanistic rationalizations three categories methods: (1) terminated by nucleophiles, (2) radicals, (3) functionality migration. 1 Introduction 2 Electrochemical Alkene Difunctionalization Terminated Nucleophiles 2.1 Sulfonylative Alkenes 2.2 Sulfurizative/Sulfoxidative 2.3 Azidotetrazolation 2.4 Trifluoromethylative 2.5 Diarylation 3 Radicals 3.1 Direct Radical-Coupling-Enabled 3.2 Metal-Mediated Radical Transfer Coupling Enabled 3.3 Metalloid-Mediated 4 Functionality Migration 5 Summary Outlook

Language: Английский

Citations

23
Electrochemical oxidative cross coupling of NH-sulfoximines with disulfides DOI
Shuai Zhang, Meiqian Hu, Changsheng Qin

et al.

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(6), P. 2576 - 2583

Published: Jan. 1, 2024

An electrochemical method for thioetherification of NH-sulfoximines with disulfides is reported. The utilization electrochemistry facilitating these reactions eliminates the necessity external oxidants, bases, and metal catalysts.

Language: Английский

Citations

11
Synthesis of Quinoxalines through Cu-electrocatalytic Azidation/Annulation Cascade at Low Catalyst Loading DOI
Mrinmay Baidya, Suman De Sarkar

Organic Letters, Journal Year: 2023, Volume and Issue: 25(31), P. 5896 - 5901

Published: July 29, 2023

A Cu-electrocatalytic azidation of N-aryl enamines and subsequent denitrogenative annulation for the construction quinoxaline frameworks is reported. Only 0.5 mol % copper(II) chloride was employed this cascade transformation displaying excellent functional-group compatibility even with complex bioactive scaffolds. The efficient electro-oxidative protocol enables use NaN3 as cheapest azide source. Detailed mechanistic experiments, cyclic voltammetry, spectroscopic studies provided strong evidence a dual role Cu catalyst in azidyl iminyl radical generation steps.

Language: Английский

Citations

20
Paraformaldehyde as C1 Synthon: Electrochemical Three‐Component Synthesis of Tetrahydroimidazo[1,5‐a]quinoxalin‐4(5H)‐ones in Aqueous Ethanol DOI
Yuhan Lu,

Si‐Yu Mu,

Jun Jiang

et al.

ChemSusChem, Journal Year: 2023, Volume and Issue: 16(19)

Published: Sept. 20, 2023

A green and practical method for the electrochemical synthesis of tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones through three-component reaction quinoxalin-2(1H)-ones, N-arylglycines paraformaldehyde was reported. In this strategy, EtOH played dual roles (eco-friendly solvent waste-free pre-catalyst) in situ generated ethoxide promoted triple sequential deprotonations.

Language: Английский

Citations

17
Electrochemical Azidocyanation of Alkenes DOI

Yun‐Tao Zheng,

Hai‐Chao Xu

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(6)

Published: Oct. 31, 2023

The difunctionalization of alkenes-a process that installs two functional groups in a single operation and transforms chemical feedstocks into value-added products-is one the most appealing synthetic methods contemporary chemistry. However, introduction distinct via readily accessible nucleophiles remains formidable challenge. Existing intermolecular alkene azidocyanation methods, which primarily focus on aryl alkenes rely stoichiometric oxidants. We report herein an unprecedented electrochemical strategy for is compatible with both alkyl alkenes. This achieved by harnessing finely-tuned anodic electron transfer strategic selection copper/ligand complexes. reactions were rendered enantioselective employing chiral ligand. Crucially, mild conditions well-regulated assure exceptional tolerance various substrate compatibility terminal internal

Language: Английский

Citations

15
Electrochemically Induced Desulfurization of Thioureas for the Synthesis of Substituted 5‐Aminotetrazoles DOI

Xiao Yu,

Liqiang Hao,

Xian Liu

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 22, 2024

Abstract A one‐pot method has been developed for synthesizing diverse substituted 5‐aminotetrazoles via the electrochemically induced desulfurizative addition–cyclization of thioureas with azidotrimethylsilane. This methodology enables construction C−N and N−N bonds under mild reaction conditions without transition metal catalysts or external oxidizing agents. The applicability this approach is demonstrated by its broad substrate scope, compatibility various functional groups, scalability to gram‐scale synthesis, practicality evidenced synthesis an antibacterial agent.

Language: Английский

Citations

5
Electrochemical Oxidative C–H Amination through a Ritter-Type Reaction DOI
Yiwen Xu, Qiang Li,

Runyou Ye

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 9518 - 9522

Published: June 1, 2023

A straightforward strategy for direct benzylic C–H bond amination via an electrochemical Ritter-type reaction is developed. The demonstrates simpler and milder conditions over the existing methods without extra mediator. Moderate to excellent yields up 94% of desired amide products were obtained with a broad substrate scope. removal Ac group by simple step can afford NH-free amines, providing suitable approach late-stage functionalization bioactive molecules.

Language: Английский

Citations

13
Electrochemical Oxidative Carbonylation of NH-Sulfoximines DOI
Mingzhe Li,

Mengyu Peng,

Wenxiu Huang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(41), P. 7529 - 7534

Published: Oct. 11, 2023

The electrochemical synthesis of N-aroylsulfoximines features the use tetra-n-butylammonium iodide (TBAI) as medium and a broad substrate scope, thus affording wide range N-aroylated sulfoximines in moderate to good yields. advantages this strategy are augmented by mild reaction conditions that external oxidant-free, ligand-free, easy scale up gram scale. Both control experiments mechanistic studies revealed whole process proceeded through palladium (II/IV/II) catalytic cycle.

Language: Английский

Citations

12
Electrochemical N-acylation and N-α-ketoacylation of sulfoximines via the selective decarboxylation and dehydration of α-ketoacids DOI
Chen Kang, Mingzhe Li, Wenxiu Huang

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(21), P. 8838 - 8844

Published: Jan. 1, 2023

We describe an electrochemical N -acylation and -α-ketoacylation of sulfoximines via the selective decarboxylation dehydration α-ketoacids using electricity as a “traceless” oxidant α-ketoacid “acyl” or “α-ketoacyl” source.

Language: Английский

Citations

11