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A base-promoted formal substitution between arylazo sulfones and amines has been developed to generate disubstituted or trisubstituted triazenes. Compared with arylazo sulfones as aryl radical precursors, this application has a higher atom utilization. This strategy offers advantages over traditional methods: stable and easy-to-store raw materials, good air compatibility, no need for light-avoiding operations. The present discovery introduces a novel nonradical application for arylazo sulfones and presents an interesting new approach to classic triazene synthesis.
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http://dx.doi.org/10.1021/acs.orglett.5c03329 | DOI Listing |
Org Lett
September 2025
Key Laboratory of Catalytic Conversion and Clean Energy in Universities of Shandong Province, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, P. R. China.
A base-promoted formal substitution between arylazo sulfones and amines has been developed to generate disubstituted or trisubstituted triazenes. Compared with arylazo sulfones as aryl radical precursors, this application has a higher atom utilization. This strategy offers advantages over traditional methods: stable and easy-to-store raw materials, good air compatibility, no need for light-avoiding operations.
View Article and Find Full Text PDFJ Org Chem
May 2025
PhotoGreen Lab, Department of Chemistry, University of Pavia, Viale Taramelli 12, 27100 Pavia, Italy.
The effect of water on visible-light-driven generation of aryl radicals or aryl cations from colored shelf-stable arylazo sulfonates has been investigated. Photoinduced ionic and radical decomposition of these salts compete, depending on the media used. In organic solvents, light-induced homolysis of the N-S bond occurs, and the resulting aryl radical may be used to some extent for arylation reactions.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur, Botanic Garden, Howrah 711103, India.
Herein, we describe a Zn-catalyzed atom-economical, inexpensive, and sustainable method for preparing a broad spectrum of substituted olefins utilizing alcohols as the main precursor. Using a Zn(II) complex [ZnLCl] () of the redox-noninnocent ligand 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline (), various ()-olefins were prepared in good yields by coupling alcohols with sulfones and aryl cyanides under an inert atmosphere. Under an aerial atmosphere, vinyl nitriles were isolated in up to 82% yield reacting alcohols with benzyl cyanides in the presence of .
View Article and Find Full Text PDFNanoscale Adv
August 2024
Istituto per la Sintesi Organica e la Fotoreattività (ISOF), Consiglio Nazionale delle Ricerche (CNR) Via P. Gobetti, 101 40129 Bologna Italy
Covalent functionalization of graphene presents a pivotal strategy to enhance its surface properties and overcome inherent chemical inertness. While diazonium salts have been extensively utilized for this purpose, their limitations necessitate exploration of alternative approaches. Arylazo sulfones, such as diazonium salt derivatives serving as chromophores, offer a promising solution, enabling photochemical reactions under visible light.
View Article and Find Full Text PDFChemistry
November 2024
Department of Pharmaceutical Sciences, School of Pharmaceutical Sciences of Ribeirão Preto, University of São Paulo (FCFRP-USP), Av. do Café, s/n° - Campus Universitário da USP, 14040-903, Ribeirão Preto/SP, Brazil.
BODIPYs have a well-established role in biological sciences as chemosensors and versatile biological markers due to their chemical reactivity, which allows for fine-tuning of their photophysical characteristics. In this work, we combined the unique reactivity of arylazo sulfones with the advantages of a "sunflow" reactor to develop a fast, efficient, and versatile method for the photochemical arylation of BODIPYs and other chromophores. This approach resulted in red-shifted emitting fluorophores due to extended electronic delocalization at the 3- and 5-positions of the BODIPY core.
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