Photoredox-Catalyzed Regioselective 1,3-Alkoxypyridylation of gem-Difluorocyclopropanes DOI
Jiaxuan Shen, Meijun Chen, Xiangwei Du

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 4, 2024

Difluoromethylene and pyridine cores are very important structural units in medicinal chemistry. Herein, we report the development of photoredox-catalyzed ring-opening 1,3-alkoxypyridylation gem-difluorinated cyclopropanes using 4-cyanopyrines alcohols, employing cyclopropane radical cations as key intermediate. The reaction exhibits high regioselectivity under mild conditions can also be practiced on gram-scale synthesis, telescoped reaction, late-stage functionalization biological molecules.

Язык: Английский

Merging Photoinduced Electron Transfer with Hydrogen Atom Transfer: Formal β-C(sp3)–H Pyridination of Carbonyls DOI
Jian Li, Jun Xu, Binbin Chen

и другие.

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

In this study, a novel approach that combines photoinduced electron transfer (ET) with hydrogen atom (HAT) has been introduced for the selective β-C(sp3)–H pyridination of carbonyl compounds. This method is notable its absence transition metals and ability to function under benign reaction conditions, resulting in range pyridinated derivatives consistently moderate good yields. The significance technique further underscored by potential late-stage functionalization pharmaceutically significant molecules. Mechanistic investigations confirmed proceeds via radical-mediated pathway.

Язык: Английский

Процитировано

5
Visible-Light-Induced Acylative Pyridylation of Styrenes DOI
Zhiqin Zhang, Jianwei Wang,

Chenfeng Yu

и другие.

Organic Letters, Год журнала: 2024, Номер 26(22), С. 4727 - 4732

Опубликована: Май 29, 2024

A visible-light-induced photocatalyst-free acylative pyridylation of styrenes with 4-acyl-1,4-dihydropyridines (DHPs) and 4-cyanopyridines has been described, featuring mild reaction conditions, a broad substrate scope, good functional group tolerance. The could also be performed under sunlight irradiation albeit slightly lower conversion. 4-Acyl-1,4-DHPs serve dual role, acting as both photoreductant to reduce the cyanopyridine its radical anion intermediate precursor produce acyl radical. mechanism was especially elucidated through Hammett analysis, quadratic linear regression analysis by using parameters, σmb σjj·. findings from further demonstrate that rate-limiting step process is single electron transfer between 4-acyl-1,4-DHPs 4-cyanopyridines.

Язык: Английский

Процитировано

8
A General Electron Donor‐Acceptor Photoactivation Using Oxime Esters Enabled Divergent Thioetherifications† DOI

Maojian Lu,

Liang‐Liang Jiang,

Yueming Xu

и другие.

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(22), С. 2751 - 2756

Опубликована: Июль 12, 2024

Comprehensive Summary The EDA complex‐mediated reactions involving oxime esters have been few studied. Herein, an complex formed by thiophenolate anion and ester is reported for photoinduced divergent synthesis of thioethers, depending on different types esters. Operational simplicity, mild reaction conditions, flexible options leaving group demonstrate the generality synthetic utility this approach. Such approach can also enable interesting thiol‐catalysis phenanthridines.

Язык: Английский

Процитировано

4
Transition-Metal and Photocatalyst-Free, Redox-Neutral Heteroarylation of C(sp3)–H Bonds DOI

Kamila Almagambetova,

Kathiravan Murugesan, Magnus Rueping

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 12664 - 12670

Опубликована: Авг. 7, 2024

Developing a transition-metal-free system for functionalizing the C(sp3)–H bond has posed long-standing challenge in synthetic organic chemistry and is of significance drug discovery. In this context, we present straightforward protocol heteroarylation benzylic alpha-amino C–H bonds, achieved without transition metals or photocatalysts. A pivotal aspect redox-neutral hydroarylation utilization commercially available triisopropylsilanethiol (iPr3SiSH) as an organocatalyst. This organocatalyst serves dual function forming electron donor–acceptor complex (EDA) acting hydrogen atom transfer catalyst, generating alkyl/benzylic radicals from corresponding bonds. Applying mild methodology, various amino bonds were functionalized to give C(sp2)–heteroaryl C–C cross-coupled product. To demonstrate practical utility protocol, pyridine was incorporated into molecule via late-stage modification. Additionally, gram-scale reaction also performed show advantages protocol.

Язык: Английский

Процитировано

4
Visible-Light-Mediated Synthesis of Anomeric S-Aryl Glycosides via Electron Donor–Acceptor Complex Using Thianthrenium Salts DOI Creative Commons

Zhuoyi Zhou,

Yufeng Zhang, Zhiqiang Yu

и другие.

Molecules, Год журнала: 2025, Номер 30(6), С. 1315 - 1315

Опубликована: Март 14, 2025

S-Aryl glycosides are not only popular glycosyl donors in carbohydrate chemistry but also serve as valuable tools various biological studies, which has brought significant attention to their preparation. However, there remains a pressing need for greener synthesis methods this area. In response, mild, sustainable, and metal- photocatalyst-free electron donor–acceptor (EDA)-mediated approach synthesizing using 1-thiosugar aryl thianthrenium salt was developed. Our strategy utilizes the donor, overcoming traditional reliance on electron-rich thiols, such or carbonyl typically required forming EDA complexes.

Язык: Английский

Процитировано

0
Visible‐Light‐Induced Three‐Component Alkylpyridylation of Alkenes Enabled by Electron Donor‐Acceptor Complex DOI
Jiaxuan Shen, Meijun Chen, Jincan Li

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(14), С. 3138 - 3143

Опубликована: Май 11, 2024

Abstract Visible‐light‐induced difunctionalization of alkenes is a powerful strategy for constructing complex molecules. Herein, we disclose three‐component 1,2‐alkylpyridylation under mild and photosensitizers‐free conditions. UV‐vis absorption spectroscopy studies NMR titration experiments indicate that the formation an EDA between 4‐alkyl‐DHPs 4‐cyanopyridines. Primary, secondary, tertiary C( sp 3 )‐centered radicals were formed by homolytic cleavage 4‐alkyl‐DHPs. Gram‐scale synthesis late‐stage functionalization medicinally relevant molecules showed synthetic potential our methodology.

Язык: Английский

Процитировано

3
Synthesis of Diarylalkanes by Photoreductive 1,2-Diarylation of Alkenes with Aryl Halides and Cyanoaromatics DOI

Liang Zeng,

Xuan‐Hui Ouyang, Deliang He

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(18), С. 13641 - 13653

Опубликована: Сен. 5, 2024

We report a visible light-induced photoreductive strategy for three-component diarylation of alkenes with aryl halides and cyanoaromatics. Upon photoredox catalysis tertiary alkyl amines as the electron transfer agent, selectively undergo halogen atom to generate radicals two C(sp

Язык: Английский

Процитировано

2
Photoredox-Catalyzed Regioselective 1,3-Alkoxypyridylation of gem-Difluorocyclopropanes DOI
Jiaxuan Shen, Meijun Chen, Xiangwei Du

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 4, 2024

Difluoromethylene and pyridine cores are very important structural units in medicinal chemistry. Herein, we report the development of photoredox-catalyzed ring-opening 1,3-alkoxypyridylation gem-difluorinated cyclopropanes using 4-cyanopyrines alcohols, employing cyclopropane radical cations as key intermediate. The reaction exhibits high regioselectivity under mild conditions can also be practiced on gram-scale synthesis, telescoped reaction, late-stage functionalization biological molecules.

Язык: Английский

Процитировано

1