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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Metal‐Free Electrochemical Carboxylation of Organic Halides in the Presence of Catalytic Amounts of an Organomediator

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

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Electrocarboxylation of Aryl Epoxides with CO₂for the Facile and Selective Synthesis of β‐Hydroxy Acids

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

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Recent progress in CO₂ conversion into organic chemicals by molecular catalysis

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(17), P. 6538 - 6560

Published: Jan. 1, 2023

An activation toolbox for the effective catalytic conversion of CO 2 to chemicals is proposed along with challenges and prospects related future development this exciting technology.

Language: Английский

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A guide to organic electroreduction using sacrificial anodes

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(4), P. 1168 - 1188

Published: Jan. 1, 2023

This review focuses on recent advances in sacrificial anode-enabled organic electroreductions.

Language: Английский

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Electroreductive Dicarboxylation of Unactivated Skipped Dienes with CO₂

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 3, 2023

Carboxylation of easily available alkenes with CO2 is highly important to afford value-added carboxylic acids. Although dicarboxylation activated alkenes, especially 1,3-dienes, has been widely investigated, the challenging unactivated 1,n-dienes (n>3) remains unexplored. Herein, we report first skipped dienes via electrochemistry, affording valuable dicarboxylic Control experiments and DFT calculations support single electron transfer (SET) reduction its radical anion, which followed by sluggish addition SET unstabilized alkyl radicals carbanions nucleophilic attack on give desired products. This reaction features mild conditions, broad substrate scope, facile derivations products promising application in polymer chemistry.

Language: Английский

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Photoredox/HAT-Catalyzed Dearomative Nucleophilic Addition of the CO₂ Radical Anion to (Hetero)Aromatics

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2482 - 2488

Published: Feb. 3, 2023

The radical anion of CO2 (CO2•–) is a strongly nucleophilic species with rapidly emerging applications in contemporary organic chemistry. This exhibits high reactivity single-electron reduction reactions due to the concomitant release stable CO2, or Giese-type reactions, especially for electron-deficient alkenes and styrene derivatives. In contrast previous reports, we herein disclose development robust method introduction CO2•–, which can be generated from cesium formate under photoredox/hydrogen atom transfer (HAT) catalysis, into heteroaromatics such as benzofuran, benzothiophene, indole derivatives afford synthetically useful α-oxy, α-thio, α-amino acid moderate yield. addition, when using naphthalene derivatives, both addition occur simultaneously produce carboxylated tetrahydronaphthalene good Moreover, one tetrahydronaphthalenes that bear cyano group was transformed corresponding γ-butyrolactam via functionality through hydrogenation followed by cyclization. To best our knowledge, these dearomative carboxylation metal formates photoredox/HAT conditions are unprecedented, thus providing synthetic option C1 source (hetero)aromatics.

Language: Английский

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Ionic Liquids in Metal, Photo-, Electro-, and (Bio) Catalysis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 5227 - 5420

Published: April 25, 2024

Ionic liquids (ILs) have unique physicochemical properties that make them advantageous for catalysis, such as low vapor pressure, non-flammability, high thermal and chemical stabilities, the ability to enhance activity stability of (bio)catalysts. ILs can improve efficiency, selectivity, sustainability bio(transformations) by acting activators enzymes, selectively dissolving substrates products, reducing toxicity. They also be recycled reused multiple times without losing their effectiveness. based on imidazolium cation are preferred structural organization aspects, with a semiorganized layer surrounding catalyst. act container, providing confined space allows modulation electronic geometric effects, miscibility reactants residence time species. stabilize ionic radical species control catalytic dynamic processes. Supported IL phase (SILP) derivatives polymeric (PILs) good options molecular engineering greener The major factors governing metal, photo-, electro-, biocatalysts in discussed detail vast literature available over past two half decades. Catalytic reactions, ranging from hydrogenation cross-coupling oxidations, promoted homogeneous heterogeneous catalysts both single multiphase conditions, extensively reviewed considering knowledge accumulated until now.

Language: Английский

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Recent Advances in Electrochemical Carboxylation with CO₂

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(18), P. 2728 - 2745

Published: Sept. 3, 2024

ConspectusCarbon dioxide (CO

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Enantioselective Nickel-Electrocatalyzed Reductive Propargylic Carboxylation with CO₂

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14864 - 14874

Published: May 16, 2024

The exploitation of carbon dioxide (CO2) as a sustainable, plentiful, and harmless C1 source for the catalytic synthesis enantioenriched carboxylic acids has long been acknowledged pivotal task in synthetic chemistry. Herein, we present current-driven nickel-catalyzed reductive carboxylation reaction with CO2 fixation, facilitating formation C(sp3)–C(sp2) bonds by circumventing handling moisture-sensitive organometallic reagents. This electroreductive protocol serves practical platform, paving way propargylic (up to 98% enantiomeric excess) from racemic carbonates CO2. efficacy this transformation is exemplified its successful utilization asymmetric total (S)-arundic acid, (R)-PIA, (S)-chizhine D, (S)-cochlearin G, (S,S)-alexidine, thereby underscoring potential electrosynthesis achieve complex molecular architectures sustainably.

Language: Английский

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