A practical electrochemically driven method for fluorosulfonylation of both aryl and alkyl thianthrenium salts has been disclosed. The strategy does not need external redox reagents or metal catalysts. In combination with C-H thianthrenation of aromatics, this method provides a new tool for the site-selective fluorosulfonylation of drugs.
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http://dx.doi.org/10.1021/acs.orglett.2c03956 | DOI Listing |
Org Lett
December 2024
Leibniz-Institut für Katalyse e.V., Albert-Einstein-Straße 29a, 18059 Rostock, Germany.
Herein, we developed a mild and efficient palladium-catalyzed carbonylative Sonogashira coupling of aryl thianthrenium salts with aliphatic alkynes and benzyl acetylene toward alkynones and furanones. Various desired products were prepared in good yields with broad functional group tolerance including the bromide group. In the case of using benzyl acetylene, the corresponding furanones can be obtained in good yields under the same conditions with two molecules of CO inserted.
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December 2024
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi 330031, China.
We have developed a novel and straightforward protocol that facilitates the transformation of alkenylsulfonium salts leading to the direct synthesis of -difluoromethylated alkenes. The success of this method relies on the use of copper catalysis and Vicic-Mikami reagent (DMPU)Zn(CFH). These mild protocols offer the advantage of selectively synthesizing either aromatic or aliphatic difluoromethylated alkenes.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
Key Laboratory of Organic Synthesis of Jiangsu Province, MOE Key Laboratory of Geriatric Diseases and Immunology, Suzhou Key Laboratory of Pathogen Bioscience and Anti-infective Medicine, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, China.
A nickel-catalyzed C-S silylation of aryl thianthrenium salts with salt-stabilized silylzinc pivalates is disclosed, thus allowing us to rapidly incorporate silyl motifs into aromatics in a site- and chemoselective fashion. This method is distinguished by its ample scope and facile derivatizations of the aryl silanes for increasing functional molecular complexity. Moreover, modular installation of silyl groups into pharmaceutically active molecules provides a new platform for the synthesis of sila-drugs.
View Article and Find Full Text PDFAdv Sci (Weinh)
November 2024
National and Local Joint Engineering Research Center of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing, 210023, P. R. China.
Efficiently assembling amino acids and peptides with bioactive molecules facilitates the modular and streamlined synthesis of a diverse library of peptide-related compounds. Particularly notable is their application in pharmaceutical development, leveraging site-selective late-stage functionalization. Here, a visible light-induced three-component reaction involving arylthianthrenium salts, amino acid/peptide derivatives, and alkenes are introduced.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470, Mülheim an der Ruhr, Germany.
Here we report the reaction of aryl thianthrenium salts that allows selective functionalization of the meta position of arenes. The combination of a site-selective thianthrenation with a Catellani reaction provides access to 3,5-dimethylated arenes. The developed reaction is complementary to the previously discovered reductive ipso-alkylation of aryl thianthrenium salts and extends the possibilities for late-stage methylation of arenes with a single aryl thianthrenium salt.
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