A facile synthesis of biologically important -aryl dithiocarbamates has been demonstrated by the aryne three-component coupling involving CS and aliphatic amines. This transition-metal-free and mild reaction is scalable and operates with good functional group compatibility. Preliminary mechanistic experiments, including density functional theory studies, are also provided. Moreover, with 3-triflyloxybenzynes, a unique four-component coupling incorporating tetrahydrofuran was observed.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.1c03378 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Cleavage of the Robust Silicon-Fluorine σ-Bond Allows Silicon-Carbon Bond Formation: Synthetic Strategies Toward Ortho-Silyl Aryl Phosphonates.
Angew Chem Int Ed Engl
September 2024
Chemical and Biological Integrative Research Center, Korea Institute of Science and Technology, 5, Hwarang-ro 14-gil, Seongbuk-gu, Seoul, 02792, Republic of Korea.
A straightforward, mild, and transition-metal-free three-component coupling reaction involving arynes, phosphites, and silyl fluorides was developed through Si-F bond activation. Although the Si-F bond is one of the strongest bonds, Si-C bond formation via Si-F bond cleavage with the assistance of bidentate silicon and phosphonium Lewis acids has been successfully achieved. This unprecedented strategy provides a facile approach for synthesizing ortho-silyl-substituted aryl phosphonates.
View Article and Find Full Text PDFIntermolecular radical oxyalkylation of arynes with alkenes and TEMPO.
Chem Sci
August 2024
Organisch-Chemisches Institut, Universität Münster Corrensstraße 40 48149 Münster Germany
Radical transformations with arynes represent an underexplored research field and only a few examples have been disclosed. In this research article, the implementation of arynes in three-component reactions with TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) and activated alkenes is demonstrated. TEMPO is added to arynes, which triggers a Meerwein-type arylation cascade where the final alkyl radial is eventually trapped by a second equivalent of TEMPO.
View Article and Find Full Text PDFTrideuteromethylthiolation through Reaction of Arynes, -Methyl- Sulfonothioate with Sulfonamides or Amides: Access to Trideuteromethylated Sulfilimines.
J Org Chem
August 2024
School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi 832003, P. R. China.
A direct and practical three-component tandem reaction of arynes, -methyl- sulfonothioate with sulfonamides or amides is developed. The reaction is highly efficient and chemoselective, which allows mild synthesis of trideuteromethylated sulfilimines with broad substrate scope and good functional group compatibility, giving the products in good to excellent yields with 92%-99% deuterium incorporation. Mechanism studies disclosed sulfenamide that generated in is the key intermediate for the reaction.
View Article and Find Full Text PDFSynthetic Strategies toward -3-propanoate Substituted Aryl Phosphonates by Three-Component Coupling Reactions of Arynes, Phosphites, and Acrylates.
J Org Chem
June 2024
Chemical and Biological Integrative Research Center, Korea Institute of Science and Technology, 5 Hwarang-ro 14-gil, Seongbuk-gu, Seoul 02792, Republic of Korea.
Mild, metal-free, and operationally simple three-component coupling reactions involving arynes, phosphites, and acrylates have been achieved. The reaction proceeded well with α- or β-substituted acrylates. Additionally, various functional groups were tolerated under these reaction conditions, resulting in diverse -3-propanoate-substituted aryl phosphonates.
View Article and Find Full Text PDFCopper-catalysed electrophilic carboamination of terminal alkynes with benzyne looked at through the computational lens.
Dalton Trans
May 2024
University of St Andrews, School of Chemistry, Purdie Building, North Haugh, St Andrews, KY16 9ST, UK.
A detailed computational mechanistic study of the copper-catalysed three-component-type electrophilic carboamination of terminal alkynes with benzyne and an archetypal -benzoylhydroxylamine electrophile is presented. Probing various plausible pathways for relevant elementary steps and scrutinising performance degradation pathways, with the aid of a reliable computational protocol applied to a realistic catalyst model combined with kinetic analysis, identified the pathways preferably traversed in productive catalysis. It entails rapid alkynylcupration of generated benzyne to deliver the arylcopper nucleophile that undergoes amination with the -benzoylhydroxylamine electrophile to afford copper benzoate.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!