Organothiocyanates and selenocyanates are valuable compounds, both in terms of functional group interconversion and due to their biological activities. In this contribution, we report the synthesis of a series of these important substances in a mixture of water and dimethyl carbonate (20/1 proportion) using potassium thio- or selenocyanates salts and organic bromides. The key to the effectiveness of the reaction is a chalcogen bond interaction between a selenonium salt catalyst and the organic substrate.
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http://dx.doi.org/10.3390/molecules28073056 | DOI Listing |
Org Biomol Chem
January 2025
Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg, 199034, Russian Federation.
The Schiff condensation between 4-methylbenzaldehyde and 2-aminopyridine, catalyzed by chloronium, bromonium, and iodonium triflates, as well as sulfonium, selenonium, and telluronium triflates, was investigated. H NMR monitoring revealed that the catalytic activity increased significantly with heavier σ-hole-bearing heteroatoms. DFT calculations showed that the maximum electrostatic potential at the σ-hole was a more reliable predictor of the catalytic activity of these organoelement species.
View Article and Find Full Text PDFChem Rec
December 2024
Department of Chemistry, Universidade Federal de Minas Gerais (UFMG), 31.270-901, Belo Horizonte, MG, Brazil.
Alkylation reactions and their products are considered crucial in various contexts. Synthetically, the alkylation of a nucleophile is usually promoted using hazardous alkyl halides. Here, we aim to highlight the potential of pnictogen (ammonium or phosphonium) and chalcogen salts (sulfonium, selenonium, and telluronium) to function as alkylating agents.
View Article and Find Full Text PDFOrg Biomol Chem
March 2024
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, P.R. China.
Molecules
April 2023
Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB T2N 1N4, Canada.
The antioxidant drug ebselen has been widely studied in both laboratories and in clinical trials. The catalytic mechanism by which it destroys hydrogen peroxide via reduction with glutathione or other thiols is complex and has been the subject of considerable debate. During reinvestigations of several key steps, we found that the seleninamide that comprises the first oxidation product of ebselen underwent facile reversible methanolysis to an unstable seleninate ester and two dimeric products.
View Article and Find Full Text PDFMolecules
March 2023
Grupo de Síntese e Catálise Orgânica-GSCO, Departamento de Química, Universidade Federal de Minas Gerais-UFMG, Belo Horizonte 31270-901, Brazil.
Organothiocyanates and selenocyanates are valuable compounds, both in terms of functional group interconversion and due to their biological activities. In this contribution, we report the synthesis of a series of these important substances in a mixture of water and dimethyl carbonate (20/1 proportion) using potassium thio- or selenocyanates salts and organic bromides. The key to the effectiveness of the reaction is a chalcogen bond interaction between a selenonium salt catalyst and the organic substrate.
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