Electro-reductive carboxylation of C Cl bonds in unactivated alkyl chlorides and polyvinyl chloride with CO2

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(12), P. 110104 - 110104

Published: June 8, 2024

Language: Английский

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Organo-mediator enabled electrochemical transformations

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review highlights organo-mediators that enable electrochemical reactions via outer-sphere electron transfer (ET), offering advantages such as availability, tunability, and simplified post-processing compared to direct electrolysis.

Language: Английский

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Visible-Light Photoredox-Catalyzed Direct Carboxylation of Tertiary C(sp³)–H Bonds with CO₂: Facile Synthesis of All-Carbon Quaternary Carboxylic Acids

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 7, 2024

Direct carboxylation of C–H bonds with CO2 represents an attractive strategy to synthesize valuable carboxylic acids high atom, step, and redox economy. Although great progress has been achieved in this field, catalytic tertiary C(sp3)–H still remains challenging due their inherent inertness significant steric hindrance. Herein, we report a direct benzylic via visible-light photoredox catalysis. Various all-carbon quaternary acids, which are importance medicinal chemistry, successfully obtained yields. This is characterized by good functional group tolerance, broad substrate scope, mild operational conditions. Furthermore, our methodology enables the efficient rapid synthesis key drug or bioactive molecules, such as carbetapentane, caramiphen, PRE-084 (σ1 receptor agonist), facilitates various functionalizations C(sp2)–H using directing ability target thus highlighting its practical applications. Mechanistic studies indicate that carbanion, serves intermediate react CO2, catalytically generated single electron reduction radical through consecutive photoinduced transfer process.

Language: Английский

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Electrochemical N–H Methylsulfoxidation of Sulfoximines with DMSO

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Comprehensive Summary The N–H methylsulfoxidation of sulfoximines using DMSO as a methylsulfinyl source, induced by electrochemistry, has been developed. This method is the first example an electrochemical reaction in which serves source. Unlike previous reactions involving substrate, exclusively proceed via radical mechanisms, this follows S‐cation pathway. A wide range N ‐methylsulfinyl were successfully obtained.

Language: Английский

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Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 21, 2025

Carboxylation with CO2 offers an attractive and sustainable access to valuable carboxylic acids. Among these methods, direct C−H carboxylation of terminal alkynes has attracted much attention for one-carbon homologation alkynes, enabling rapid synthesis propiolic In contrast, the multi-carbons construct important non-conjugated alkynyl-containing acids not been reported. Herein, we present alkynylcarboxylation alkenes via photoredox copper dual catalysis. This protocol provides a practical method form alkynyl from readily available CO2. Additionally, this approach also features mild (room temperature, 1 atm CO2) redox-neutral conditions, high atom step economy, good functional group tolerance, selectivities. Moreover, diverse transformations β-alkynyl acid products bioactive molecule (GPR40/FFA1 agonist) further illustrate synthetic utility methodology. The report multi-carbon is rare. authors catalysis, affording

Language: Английский

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Selective carboxylation of alkenes with CO2 to form unsaturated carboxylic acid on Sc-exchanged MFI zeolite

Catalysis Today, Journal Year: 2025, Volume and Issue: unknown, P. 115321 - 115321

Published: April 1, 2025

Language: Английский

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Synthetic application of oxalate salts for visible-light-induced radical transformations

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111224 - 111224

Published: April 1, 2025

Language: Английский

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Nickel‐Catalyzed Atroposelective Carbo‐Carboxylation of Alkynes with CO2: En Route to Axially Chiral Carboxylic Acids

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Nov. 7, 2024

Abstract Precise synthesis of carboxylic acids via catalytic carboxylation with CO 2 is highly appealing. Although considerable advancements have been achieved in difunctionalizing unsaturated hydrocarbons, the asymmetric variants are conspicuously underdeveloped, particularly addressing axially chiral alkenes. Herein, we report first atroposelective alkynes . A variety valuable obtained good yields and high chemo‐, regio‐, Z/E enantio‐selectivities. Notably, an unexpected anti ‐selective carbo‐carboxylation observed sp ‐hybrid carbo‐electrophile‐initiated reductive alkynes. Mechanistic studies including DFT calculation elucidate origin induction ‐selectivity vinyl‐carboxylation

Language: Английский

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Electrochemical conversion of CO₂ via C−X bond formation: recent progress and perspective

Chemical Synthesis, Journal Year: 2024, Volume and Issue: 4(4)

Published: Oct. 9, 2024

With the depletion of traditional energy sources and growing environmental concerns, it is becoming increasingly urgent to develop green, low-emission renewable technologies replace fossil fuel-driven methods that emit carbon dioxide (CO2). Currently, electrochemical production high-value-added chemicals fuels from CO2 has aroused great interest scientists. However, make full use for preparation chemicals, necessary expand range electrosynthesis methods, in particular by expanding reaction pathways through with different substrates. In general, can form new covalent bonds substrate molecules formation C−X bonds, including C−H, C−C, C−N, C−O, C−S which would possible products diversifying pathway. this review, we focus on research progress conversion bond formation. We start examining fundamentals reactions summarizing modes. Next, discuss (C−H, C−S) using molecules. Finally, (i) strategies design activity optimization catalyst materials (ii) future development forming five types small are discussed, along an outlook their prospects.

Language: Английский

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Integrating Umpolung and CO₂ Shuttling Strategies for the Synthesis of ¹²C- and ¹³C-α-Ketoacids from Aldehydes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(41), P. 8967 - 8972

Published: Oct. 9, 2024

The direct carboxylation of aldehydes with CO2 is rare due to the polarity mismatch between these two electrophilic substrates. To address this challenge, we propose a sequential approach for synthesizing α-ketoacids from commercially available by integrating umpolung and shuttling strategies. This transition metal-free shuttle method enables transfer triphenylacetic acid potassium salt thioacetal, eliminating need handling pressurized gas or using specialized equipment, while also enhancing reaction's functional group tolerance. Furthermore, use stoichiometric slightly excess amounts as formal donor makes it suitable complete 13C labeling α-ketoacids.

Language: Английский

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