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

Decatungstate‐Photocatalyzed Diastereoselective Dearomative Hydroalkylation of Indoles DOI Creative Commons

Emeric Montinho‐Inacio,

Damien Bouchet, Wei‐Yang Ma

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(22)

Published: April 16, 2024

Abstract In this study, we present an efficient and straightforward dearomative hydroalkylation of indoles. By utilizing alkanes or ethers as alkyl radical sources employing TBADT a cost‐effective photocatalyst for direct hydrogen atom transfers (HAT), achieved successful conversion these heterocyclic derivatives into 2‐alkylindolines with good to excellent yields high diastereoselectivity under mild reaction conditions.

Language: Английский

Citations

8
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

5
Formate Salts: The Rediscovery of Their Radical Reaction under Light Irradiation Opens New Avenues in Organic Synthesis DOI

Qing Shen,

Kun Cao,

Xiaoqing Wen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(21), P. 4274 - 4293

Published: Aug. 17, 2024

Abstract Formates are abundantly available and inexpensive commodity chemical, widely used in laboratory industrial organic synthesis. promising hydrogen carrier green C1 source, have also been a subject of research as SET reductants recent years. Compared to the toxic flammable gas carbon monoxide, which serves formates easier handle, store, transport, more environmentally friendly. Therefore, studies radical reactions, formate is not only an ideal source carbonyl, great significance synthesize carboxyl compounds with various structures, but reductant for editing molecules either scientific or production. The activation conversion formate, reductant, very challenging hot field

Language: Английский

Citations

4
Formate‐Mediated Synthesis of β‐Hydroxysulfides from Olefins and Thiosulfonates via EDA Complex Strategy under Visible Light Irradiation in Air DOI

Qing Shen,

Xiaoyan Peng,

Jiahong Sui

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(23), P. 3129 - 3134

Published: Aug. 13, 2024

Comprehensive Summary A visible‐light‐induced and efficient one‐pot synthesis of β ‐hydroxysulfides from olefins, thiosulfonates HCOOCs using an EDA complex strategy under air atmosphere at room temperature has been disclosed. plausible radical involved mechanism is proposed. During the reaction process, formates play a crucial role: first, as donors in complex; second, providers hydrogen source; third, by generating CO 2 •– to reduce peroxide intermediates, leading formation ‐hydroxysulfides. In contrast previously reported thiol‐oxygen co‐oxidation reactions, this simple sustainable approach features mild conditions, operational simplicity, odorless excellent functional group tolerance.

Language: Английский

Citations

3
1‐Methylpyridine‐2(1H)‐thione Photocatalyzed Giese Reaction with N‐Hydroxyphthalimide Esters via Single Electron Transfer DOI Open Access

Lanting Li,

Yuzhuo Wang, Li Yuan

et al.

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

Published: Jan. 18, 2025

Comprehensive Summary We have developed a series of 1‐methylpyridine‐2(1 H )‐thione (MPT) analogues to be used as organocatalysts. The MPT catalysts are easily prepared and bench‐stable. In our previous work, we found that the ground‐state catalyst could act nucleophile generate primary radicals via an S N 2 pathway. However, this reaction was limited benzyl radicals. Herein, reported new catalytic property catalyst. photoexcited ( E (MPT ·+ /MPT*) = –1.60 V vs. Ag/AgCl in MeCN) reduce NHPI esters through single electron transfer process. Various carbon radicals, including radical, well primary, secondary tertiary alkyl generated easily. Notably, amino acids, peptide, pharmaceuticals, other biologically active molecules modified by using methodology showing potential synthetic utility method.

Language: Английский

Citations

0
HDAC inhibitor SAHA triggers the production of previously undescribed sesquiterpenes and undergoes biotransformation by the fungus Robillarda sessilis from Verbena officinalis L. DOI

Liangxiu Liao,

Junguo Huang,

Zhu Tao

et al.

Phytochemistry, Journal Year: 2025, Volume and Issue: unknown, P. 114411 - 114411

Published: Jan. 1, 2025

Language: Английский

Citations

0
Visible-Light Photoredox-Catalyzed Carboxylation of Benzylic C(sp3)–O Bonds in Ethers with CO2 DOI
Jingwei Yang,

Chuan‐Kun Ran,

Wenjing Zhu

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: June 5, 2025

Although significant progress has been made in achieving site-selective C-O bond functionalization specific substrates, the selective cleavage and of C(sp3)-O bonds ethers remain a fundamental challenge synthetic chemistry. Herein, we present an efficient carboxylation method via photoredox-catalyzed benzylic with carbon dioxide (CO2). Diverse primary, secondary, tertiary benzyl undergo CO2 to generate valuable aryl acetic acids, including several drug molecules. This photocatalyzed reaction is operationally simple implement versatile for various ethers, exhibiting favorable compatibility diverse functional groups. Mechanistic studies indicate that single electron transfer (SET) reduction might be key generating highly reactive radical anion intermediate, which could another SET process carbanions CO2.

Language: Английский

Citations

0
Nucleophilic Organocatalyst for Photochemical Carbon Radical Generation via SN2 Substitution DOI
Yuzhuo Wang,

Shiwen Fan,

Xinjun Tang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 4002 - 4007

Published: May 1, 2024

Photochemical generation of radicals is a powerful way to construct various molecules. But most these methods rely on initiators or the redox properties radical precursors. Herein, we report photochemical organic catalyst that reacts with benzyl halide generate carbon via an SN2 pathway. This nucleophilic can be easily prepared and bench-stable. The process does not halides, showing potential synthetic utility. Control experiments UV–vis spectroscopic analysis indicate substitution adduct key intermediate.

Language: Английский

Citations

2
Photoinduced Radical Approach for Desulfurative Alkylation of Cysteine Derivatives to Make Unnatural Amino Acids DOI
Pei Xu, Yiqin Liu,

Hui-Xian Jiang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 4, 2024

Unnatural amino acids (UAAs) are highly valuable molecules in organic synthesis, pharmaceutical sciences, and material science. Herein, we present a photocatalytic radical approach for desulfurative alkylation of cysteine derivatives with arenethiol as the hydrogen atom transfer catalyst making UAAs peptides. The formate salt, acting donor, situ generates reductive CO

Language: Английский

Citations

2
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

Citations

2