Single-Electron-Transfer-Generated Aryl Sulfonyl Ammonium Salt: Metal-Free Photoredox-Catalyzed Modular Construction of Sulfonamides DOI
Fengying Yan, Qing Li,

Shanshan Fu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5227 - 5235

Published: March 21, 2024

Sulfonamides are prominently featured in organic synthesis and medicinal chemistry. Yet, a general synthetic platform for the modular construction of aryl sulfonamides remains elusive. Herein, metal-free photoredox-catalyzed three-component via an sulfonyl ammonium salt intermediate, which was generated situ SET event, has been established. A variety structurally diverse primary, secondary, tertiary were synthesized rapidly from abundant amines or sodium azide under mild conditions. Notably, primary aliphatic amine, challenging Cu-catalyzed protocols, worked well this approach. Moreover, fluoride can be accessed smoothly as well, using potassium hydrogen nucleophile. The potential utility conversion is demonstrated facile three bioactive drug compounds. Preliminary mechanistic studies have revealed that radical key intermediates mechanistically innovative methodology.

Language: Английский

Thianthrenium-Enabled Phosphorylation of Aryl C–H Bonds via Electron Donor–Acceptor Complex Photoactivation DOI
Hao Xu, Xufeng Li,

Yuzheng Dong

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(20), P. 3784 - 3789

Published: May 16, 2023

An efficient strategy for the preparation of aryl phosphonates via blue-light-promoted single electron transfer process an EDA complex between phosphites and thianthrenium salts has been demonstrated. The corresponding substituted were obtained in good to excellent yields, byproduct thianthrene can be recovered reused quantity. This developed method realizes construction through indirect C-H functionalization arenes, which potential application value drug discovery development.

Language: Английский

Citations

42
Synthetic Applications of Sulfonium Salts as Aryl Radical Precursors DOI Open Access

Xinyin Wu,

Pan Gao, Feng Chen

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(43)

Published: Sept. 13, 2023

Abstract The utilization of aryl radicals as open‐shelled intermediates has become an essential tool for both conventional and state‐of‐the‐art synthetic chemistry. However, the current methods generating are still inefficient, greatly impeding their practical applications. Encouragingly, sulfonium salts have emerged appealing sources a wide range transformations aimed at creating novel chemical bonds driven by distinctive structural attributes tendencies. This review primarily focuses on specific reaction mechanisms underlying cleavage C−S in salts, leading to generation corresponding within diverse conditions.

Language: Английский

Citations

39
Direct Synthesis of Sulfonamides via Synergetic Photoredox and Copper Catalysis DOI
Mingjun Zhang, Lixia Liu, Beibei Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(17), P. 11580 - 11588

Published: Aug. 18, 2023

Despite the frequent occurrence of sulfonamides in contemporary pharmaceuticals and agrochemicals, synthesis these compounds is limited by availability preexisting sulfur functionality, amine nucleophilicity, functional group compatibility. Herein, we report use synergetic photoredox copper catalysis to synthesize from a variety aryl radical precursors, readily available amines, dioxide source air at room temperature. The reactions proceeded smoothly with various electron-rich electron-deficient amines generate single-step process. Oxygen was deemed be essential for both catalytic cycles, acting as catalyst. Experimental studies, including electron paramagnetic resonance spectroscopy, provided insights into possible mechanism.

Language: Английский

Citations

38
Polarity Transduction Enables the Formal Electronically Mismatched Radical Addition to Alkenes DOI Creative Commons

Subhasis Paul,

Dario Filippini, Mattia Silvi

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(5), P. 2773 - 2778

Published: Jan. 31, 2023

The formation of carbon-carbon bonds via the intermolecular addition alkyl radicals to alkenes is a cornerstone organic chemistry and plays central role in synthesis. However, unless specific electrophilic are involved, polarity matching requirements restrict alkene component be electron deficient. This limits scope fundamentally important bond forming process that could otherwise more universally applied. Herein, we introduce

Language: Английский

Citations

34
Organophotocatalytic Mechanisms: Simplicity or Naïvety? Diverting Reactive Pathways by Modifications of Catalyst Structure, Redox States and Substrate Preassemblies DOI Creative Commons
Mark John P. Mandigma, Jaspreet Kaur, Joshua P. Barham

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(11)

Published: Feb. 21, 2023

Abstract Photocatalysis is a powerful tool to assemble diverse chemical scaffolds, yet bottleneck on its further development the understanding of multitude possible pathways when practitioners rely only oversimplified thermodynamic and optical factors. Recently, there growing number studies in field that exploit, inter alia , kinetic parameters organophotocatalysts are synthetically more programmable terms their redox states opportunities for aggregation with target substrate. Non‐covalent interactions play key role enables access new generation reactivities such as those open‐shell organophotocatalysts. In this review, we discuss how targeted structural modifications influence organophotocatalytic mechanisms together underlying principles. We also highlight benefits strategies preassembly static quenching overcome common reactivity issues (e. g., diffusion rate limits energetic limits).

Language: Английский

Citations

31
Triarylamines as catalytic donors in light-mediated electron donor–acceptor complexes DOI Creative Commons
Durbis J. Castillo‐Pazos, Juan D. Lasso, Ehsan Hamzehpoor

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(13), P. 3470 - 3481

Published: Jan. 1, 2023

Recently, photochemistry of Electron Donor-Acceptor (EDA) complexes employing catalytic amounts electron donors have become interest as a new methodology in the catalysis field, allowing for decoupling transfer (ET) from bond-forming event. However, examples practical EDA systems regime remain scarce, and their mechanism is not yet well-understood. Herein, we report discovery an complex between triarylamines α-perfluorosulfonylpropiophenone reagents, catalyzing C-H perfluoroalkylation arenes heteroarenes under visible light irradiation pH- redox-neutral conditions. We elucidate this reaction using detailed photophysical characterization complex, resulting triarylamine radical cation, its turnover

Language: Английский

Citations

31
A General Electron Donor–Acceptor Photoactivation Platform of Diaryliodonium Reagents: Arylation of Heterocycles DOI

Prahallad Meher,

Satya Prakash Panda,

Sanat Kumar Mahapatra

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(46), P. 8290 - 8295

Published: Nov. 14, 2023

We report a photoredox system comprising sodium iodide, triphenyl phosphine, and N,N,N',N'-tetramethylethylenediamine (TMEDA) that can form self-assembled tetrameric electron donor-acceptor (EDA) complex with diaryliodonium reagents (DAIRs) furnish aryl radicals upon visible light irradiation. This practical mode of activation DAIRs enables arylation an array heterocycles under mild conditions to provide the respective heteroaryl-(hetero)aryl assembly in moderate excellent yields. Detailed mechanistic investigations photophysical DFT studies provided insight into reaction mechanism.

Language: Английский

Citations

29
Thianthrene Radical Cation as a TransientSETMediator: Photoinduced Thiocyanation and Selenocyanation of Arylthianthrenium Salts† DOI

Xiao‐Yue Chen,

Xin Kuang,

Yichen Wu

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(16), P. 1979 - 1986

Published: April 5, 2023

Comprehensive Summary A novel transient SET mediator approach has been developed for the photoinduced radical‐radical cross coupling reaction. Using in‐situ generated thianthrene radical cation as mediator, thiocyanation and selenocyanation of aryl thianthrenium salts have realized under mild conditions without need photocatalyst or single electron donor. In comparison with enabled process, protocol features conditions, simple manipulation, a broad substrate scope, excellent functional group heterocycle tolerance. Due to feasible accessibility salts, this method also applied in efficient synthesis bioactive molecule, late‐stage functionalization complex arenes.

Language: Английский

Citations

27
Aryl sulfonium salt electron donor-acceptor complexes for halogen atom transfer: Isocyanides as tunable coupling partners DOI Creative Commons
Huaibo Zhao,

Valentina Dafnae Cuomo,

James A. Rossi‐Ashton

et al.

Chem, Journal Year: 2024, Volume and Issue: 10(4), P. 1240 - 1251

Published: Feb. 13, 2024

The photoactivation of sulfonium salt EDA (electron donor-acceptor) complexes provides a mild platform for aryl-radical-mediated halogen atom transfer activation wide range functionalized alkyl iodides, including tertiary iodides. Using an aryl with carbonate as inexpensive donor complex formation, the general reaction has been applied in divergent, metal-free photochemical approach to nitriles and amides. This divergency was made possible by tuning isocyanide radical traps. For example, identification readily accessible, bench-stable, crystalline amide containing grants access nitrile products complete selectivity.

Language: Английский

Citations

16
Generation and Application of Aryl Radicals Under Photoinduced Conditions DOI
Anupam Das, K. R. Justin Thomas

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(31)

Published: March 28, 2024

Abstract Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon‐carbon and carbon‐heteroatom bonds. The synthetic applications photoinduced complex compounds, including natural products, physiologically significant molecules, functional materials, have received immense attention. An overview current developments production methods their uses given this article. A generalized idea how to choose reagents approach for radicals described, along with techniques associated mechanistic insights. Overall, article offers critical assessment results as well selection reaction parameters specific context cascades, cross‐coupling reactions, functionalization, selective C−H functionalization substrates.

Language: Английский

Citations

15