Electrochemical generation of nitrogen-centered radicals for organic synthesis

Green Synthesis and Catalysis, Journal Year: 2021, Volume and Issue: 2(2), P. 165 - 178

Published: March 29, 2021

There is a resurgence of interests in organic electrochemistry, which generally accepted as green synthetic tool. In this context, many electrochemical methods have been developed the past decade to access various nitrogen-centered radicals (NCRs) from readily available precursors controlled fashion, enabling rapid development NCR-mediated new reactions for construction nitrogen-containing compounds. review, recent advances chemistry electrochemically generated NCRs are critically highlighted, based on strategies their formation and types NCRs. Focus put mechanism generation different applications.

Language: Английский

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Aminoxyl-Catalyzed Electrochemical Diazidation of Alkenes Mediated by a Metastable Charge-Transfer Complex

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(7), P. 2825 - 2831

Published: Jan. 23, 2019

We report the development of a new aminoxyl radical catalyst, CHAMPO, for electrochemical diazidation alkenes. Mediated by an anodically generated charge-transfer complex in form CHAMPO-N3, was achieved across broad scope alkenes without need transition metal catalyst or chemical oxidant. Mechanistic data support dual catalytic role serving as both single-electron oxidant and group transfer agent.

Language: Английский

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Electrochemical Dearomative 2,3-Difunctionalization of Indoles

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(7), P. 2832 - 2837

Published: Jan. 23, 2019

We report the use of electrochemistry to perform a direct oxidative dearomatization indoles leading 2,3-dialkoxy or 2,3-diazido indolines under undivided conditions at constant current. This operationally simple electro-oxidative procedure avoids an external oxidant and displays excellent functional group compatibility. The formation two C-O C-N bonds is believed arise from oxidation into radical cation intermediates.

Language: Английский

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Recent Advances on the Electrochemical Difunctionalization of Alkenes/Alkynes

Chinese Journal of Chemistry, Journal Year: 2019, Volume and Issue: 37(3), P. 292 - 301

Published: Feb. 6, 2019

Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which considered as one the green and efficient methods attracts growing attention. In this review, we summarized comprehensively recent literature reports on electrochemical oxidative difunctionalization unsaturated C—C bonds. The reaction types described review included intermolecular cyclization, intramolecular alkenes/alkynes. This focuses discussion its synthetic generality for preparation functionalized compounds related mechanism.

Language: Английский

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Electrochemical Late-Stage Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335

Published: Sept. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Language: Английский

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New Strategies for the Synthesis of Aliphatic Azides

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(7), P. 4253 - 4307

Published: Feb. 26, 2021

Aliphatic azides are a versatile class of compounds found in variety biologically active pharmaceuticals. These also recognized as useful precursors for the synthesis range nitrogen-based scaffolds therapeutic drugs, compounds, and functional materials. In light growing importance aliphatic both chemical biological sciences, vast array synthetic strategies preparation structurally diverse have been developed over past decades. However, to date, this topic has not subject dedicated review. This review aims provide concise overview modern access that emerged since 2010. The discussed azidation reactions include (a) C–C multiple bonds, (b) C–H (c) direct transformation vinyl into other azides, (d) miscellaneous azides. We critically discuss outcomes generality uniqueness different mechanistic rationale each selected reactions. challenges potential opportunities outlined.

Language: Английский

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Unlocking the Potential of High-Throughput Experimentation for Electrochemistry with a Standardized Microscale Reactor

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(8), P. 1347 - 1355

Published: Aug. 5, 2021

Organic electrochemistry has emerged as an enabling and sustainable technology in modern organic synthesis. Despite the recent renaissance of electrosynthesis, broad adoption synthetic community, especially industrial settings, been hindered by lack general, standardized platforms for high-throughput experimentation (HTE). Herein, we disclose design HT

Language: Английский

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Organic Synthesis Using Nitroxides

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10302 - 10380

Published: Aug. 14, 2023

Nitroxides, also known as nitroxyl radicals, are long-lived or stable radicals with the general structure R1R2N–O•. The spin distribution over nitroxide N and O atoms contributes to thermodynamic stability of these radicals. presence bulky N-substituents R1 R2 prevents radical dimerization, ensuring their kinetic stability. Despite reactivity toward various transient C some nitroxides can be easily stored under air at room temperature. Furthermore, oxidized oxoammonium salts (R1R2N═O+) reduced anions (R1R2N–O–), enabling them act valuable oxidants reductants depending on oxidation state. Therefore, they exhibit interesting across all three states. Due fascinating properties, find extensive applications in diverse fields such biochemistry, medicinal chemistry, materials science, organic synthesis. This review focuses versatile For use other important fields, we will refer several articles. introductory part provides a brief overview history chemistry. Subsequently, key methods for preparing discussed, followed by an examination structural diversity physical properties. main portion this is dedicated reactions, wherein parent corresponding serve active species. It demonstrated that functional groups (such alcohols, amines, enolates, alkanes among others) efficiently oxidized. These oxidations carried out using catalysts combination stoichiometric terminal oxidants. By reducing anions, become effective reagents intriguing Nitroxides possess ability selectively react making useful terminating cascade reactions forming alkoxyamines. Depending structure, alkoxyamines weak C–O bonds, allowing thermal generation through reversible bond cleavage. Such thermally generated participate transformations, discussed end review. application strategy natural product synthesis presented.

Language: Английский

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Regioselective aliphatic C–H functionalization using frustrated radical pairs

Nature, Journal Year: 2023, Volume and Issue: 619(7970), P. 514 - 520

Published: July 5, 2023

Language: Английский

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Cathode Material Determines Product Selectivity for Electrochemical C−H Functionalization of Biaryl Ketoximes

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(46), P. 15153 - 15156

Published: Sept. 18, 2018

Abstract The synthesis of polycyclic N‐heteroaromatic compounds and their corresponding N‐oxides has been developed through electrochemical C−H functionalization biaryl ketoximes. oxime substrates undergo dehydrogenative cyclization when a Pt cathode is used, resulting in unprecedented access to wide range N‐oxides. products the electrosynthesis are switched deoxygenated N‐heteroaromatics by employing Pb sequential anode‐promoted cathodic cleavage N−O bond initially formed N‐oxide.

Language: Английский

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