Visible-Light-Driven Carboxylative 1,2-Difunctionalization of C═C Bonds with Tetrabutylammonium Oxalate DOI Creative Commons

Sai Wang,

Pei Xu, Zhitao Liu

et al.

ACS Central Science, Journal Year: 2024, Volume and Issue: 11(1), P. 46 - 56

Published: Nov. 15, 2024

Herein, we report a visible-light-induced charge-transfer-complex-enabled dicarboxylation and deuterocarboxylation of C═C bonds with oxalate as masked CO2 source under catalyst-free conditions. In this reaction, disclosed the first example that tetrabutylammonium could be able to aggregate aryl substrates via π–cation interactions form charge transfer complexes, which subsequently triggers single electron from oxalic dianion ammonium countercation irradiation 450 nm bule LEDs, releasing radical anions. Diverse alkenes, dienes, trienes, indoles, including challenging trisubstituted olefins, underwent anti-Markovnikov high selectivity access valuable 1,2- 1,4-dicarboxylic acids well indoline-derived diacids β-deuterocarboxylic mild The in situ generated CO2•– molecules anions both add bond without assistance any photocatalyst or additives, made reaction sustainable, clean, efficient.

Language: Английский

Photocatalytic deuterocarboxylation of alkynes with oxalate DOI Creative Commons

Pei Xu,

Hao-Qiang Jiang,

Hui Xu

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(32), P. 13041 - 13048

Published: Jan. 1, 2024

Herein, a catalytic photoredox-neutral strategy for alkyne deuterocarboxylation with tetrabutylammonium oxalate as the carbonyl source and D

Language: Английский

Citations

5
Visible Light-Induced Cobalt-Catalyzed 1,3-Diphosphination of Alkenes DOI

Wenlong Shan,

Zemin Wang,

Chenxia Gao

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(18), P. 9749 - 9756

Published: Jan. 1, 2024

A novel cobalt-catalyzed radical 1,3-diphosphination of alkenes was developed, which enables straightforward access to 1,3-diphosphine skeleton compounds under mild conditions.

Language: Английский

Citations

5
Visible-Light Photoredox-Catalyzed Direct Carboxylation of Tertiary C(sp3)–H Bonds with CO2: Facile Synthesis of All-Carbon Quaternary Carboxylic Acids DOI

Yi Liu,

Guan-Hua Xue,

Zhen He

et al.

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

Citations

5
Visible-Light-Promoted Cascade Carboxylation/Arylation of Unactivated Alkenes with CO2 for the Synthesis of Carboxylated Indole-Fused Heterocycles DOI

Yang Han,

Qi Yang,

Yang Yao

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(30), P. 6341 - 6346

Published: July 18, 2024

Described here is a visible-light-promoted cascade carboxylation/arylation of indole-tethered unactivated alkenes with CO

Language: Английский

Citations

4
Photoredox-Neutral Deoxygenative Carboxylation of Acylated Alcohols with Tetrabutylammonium Oxalate DOI

Chen-Wei Xu,

Si-Yi Yan,

Hui Xu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 11967 - 11973

Published: July 26, 2024

Herein, a photoredox-neutral strategy for carboxylation of acylated alcohols via C(sp3)–O bond activation and cleavage with tetrabutylammonium oxalate (TBAO) as the carbonyl source reductant well promoter is described. Neither pre-established CO2 atmosphere nor external electron donors are required TBAO crucial transformation. Various primary, secondary, tertiary could be smoothly converted to corresponding aryl acetic acids, which core structures diverse pharmaceutical drugs.

Language: Английский

Citations

4
Photocatalytic 1,3-Difluoroalkylcarboxylation of Alkenes by Triple Kinetic-Controlled Radical Self-Ordering DOI Creative Commons

Hong Fu,

Zuo-Shuai Wang,

Sijia Li

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A transition-metal-free protocol for the unsymmetrical radical 1,3-difunctionalization of alkenes has been established first time in form 1,3-difluoroalkylcarboxylation by a photocatalytic three-component reaction allyl formates, trifluoroacetanilides, and cesium formate. This employs formate as carboxylating reagent trifluoroacetanilide difluoroalkylating via C-F bond activation. As result, series previously inaccessible difluorinated adipic acid derivatives can be easily efficient prepared. Mechanism studies reveal that triple kinetic-controlled self-ordering is key to this unique reaction. sorting involves fast initiation CO2 anion its chemoselective addition reduction, followed slow generation fluoroalkyl chemo-/regioselective addition. Notably, strategy also suitable cyclic through diastereoselectively constructing two or three consecutive stereocenters.

Language: Английский

Citations

0
Nickel‐Catalyzed LiCl‐Controlled Switchable Carboxylation of Aryl C—F Bonds with One or Two Molecules of CO2 DOI Open Access

Chunzhe Pei,

Shanglin Han,

Hanxuan Wu

et al.

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

Published: March 7, 2025

Comprehensive Summary The use of CO 2 as a renewable C1 source for the synthesis value‐added chemicals can contribute to more sustainable chemistry. In this work, nickel‐catalyzed amide‐directed carboxylation aryl C−F bonds with has been developed. reaction is switchable controlled by LiCl react one or two molecules afford valuable phthalimides α‐hydroxycarboxylic acid derivatives. Further study shows that step‐by‐step process. first step and tandem cyclization phthalimides. second C−N bond , intramolecular nucleophilic addition amide anion carbonyl. also developed based on reaction. work features inert functionalization, activation, multiple incorporation. Mechanistic studies indicate azanickelacycle intermediates play an important role, facilitates reduction Ni(II) Ni(I) promotes molecule . This protocol provides efficient route functionalization under mild conditions via chemical fixation

Language: Английский

Citations

0
Reduction by Oxidation: Selective Hydrodehalogenation of Aryl Halides by Mediated Oxalate Oxidation DOI
Joshua A. Beeler,

Rune P. Walkingshaw,

Safiya A.S. Hamud

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

Electro-organic reduction reactions are canonically carried out at a cathode which significant negative potential is applied. Specifically, carbon electrodes, aryl bromides and chlorides undergo heterogeneous in organic solvents potentials more than −2 V vs E0′ for the Fc/Fc+ couple (Fc = ferrocene). To decrease overpotential reactions, homogeneous or electrocatalysis strategies often employed. Here, we present an electrochemical method to reduce that initiated by oxidation reaction very mild (∼0 Fc/Fc+). of outer-sphere redox mediator, 1,1-dimethylferrocene, dry N,N-dimethylformamide (DMF) containing oxalate (C2O42–), results one-electron C2O42–. The resulting C2O4•– decomposes ∼1 μs release dioxide radical anion (CO2•–), potent reductant oxidized CO2 –2.68 Fc/Fc+. In this way, low electrode enables chlorides, otherwise directly reduced potentials. Using method, selective hydrodehalogenations electron-deficient reticulated vitreous anode with up quantitative conversion yields. Cyclic voltammetry finite difference simulations used characterize hydrodehalogenation 4-bromobenzonitrile via C2O42– oxidation. Additionally, show efficiency tuned deliberate additions water DMF solutions, leading substantial improvement overall yields without interference from proton reduction.

Language: Английский

Citations

0
Synthetic application of oxalate salts for visible-light-induced radical transformations DOI

Hui-Xian Jiang,

Zhitao Liu, Pei Xu

et al.

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

Published: April 1, 2025

Language: Английский

Citations

0
Taming CO2•– via Synergistic Triple Catalysis in Anti-Markovnikov Hydrocarboxylation of Alkenes DOI
Pintu Ghosh,

Sudip Maiti,

Augustin Malandain

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(44), P. 30615 - 30625

Published: Oct. 29, 2024

The direct utilization of carbon dioxide as an ideal one-carbon source in value-added chemical synthesis has garnered significant attention from the standpoint global sustainability. In this regard, photo/electrochemical reduction CO

Language: Английский

Citations

3