Cross-coupling reactions of unactivated aryl sulfides with alkynylmagnesium chloride have been invented to afford 1-aryl-1-alkynes with the aid of a palladium/N-heterocyclic carbene complex. This reaction has by far the widest scope of all transformations utilizing aryl sulfides and alkynes, while known cross-coupling alkynylations of aryl-sulfur electrophiles require activated azaaryl sulfides, thiolactams, or arenesulfonyl chlorides. The alkynylation of aryl sulfides is compatible with typical protecting functional groups. The alkynylation is applied to the synthesis of benzofuran-based fluorescent molecules by taking advantage of characteristic organosulfur chemistry.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/chem.201602315 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Water-soluble platinum and palladium porphyrins with peripheral ethyl phosphonic acid substituents: synthesis, aggregation in solution, and photocatalytic properties.
Dalton Trans
January 2025
Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR 6302 CNRS, Université de Bourgogne, 9 Avenue Alain Savary, BP 47870, 21078 Dijon Cedex, France.
Water-soluble porphyrins have garnered significant attention due to their broad range of applications in biomedicine, catalysis, and material chemistry. In this work, water-soluble platinum(II) and palladium(II) complexes with porphyrins bearing ethyl phosphonate substituents, namely, Pt/Pd 10-(ethoxyhydroxyphosphoryl)-5,15-di(-carboxyphenyl)porphyrins (M3m, M = Pt(II), Pd(II)) and Pt/Pd 5,10-bis(ethoxyhydroxyphosphoryl)-10,20-diarylporphyrins (M1d-M3d; aryl = -tolyl (1), mesityl (2), -carboxyphenyl (3)), were synthesized by alkaline hydrolysis of the corresponding diethyl phosphonates M6m and M4d-M6d. NMR, UV-vis, and fluorescence spectroscopy revealed that the mono-phosphonates M3m tend to form aggregates in aqueous media, while the bis-phosphonates M3d exist predominantly as monomeric species across a wide range of concentrations (10-10 M), ionic strengths (0-0.
View Article and Find Full Text PDFEnergy Transfer (EnT)-Mediated Stereoselective Aryl-Heterofunctionalization of Unactivated Alkynes via Radical Rearrangement.
J Org Chem
January 2025
Institute of Materia Medica, School of Pharmaceutical Sciences, Nanjing Tech University, Nanjing 211816, P. R. China.
In this study, we present a novel catalyst-free energy transfer mediated radical rearrangement strategy for the aryl-heterofunctionalization of unactivated alkynes, leading to the synthesis of polyfunctional olefins with exceptional stereoselectivity. This innovative approach, driven by visible light, exemplifies green chemistry principles by eliminating the reliance on transition metals, external oxidants, and photocatalysts. The broad applicability of our method is demonstrated through the successful synthesis of a diverse array of compounds, including vinyl sulfones, vinyl selenides, and vinyl sulfides.
View Article and Find Full Text PDFCollaborative Reduction-Induced Nickel-Catalytic Selective C-S Coupling of Aryl Di/Trithiosulfonates with Aryl Halides.
Org Lett
January 2025
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710127, People's Republic of China.
Metal-catalytic conversion of polysulfide reagents is a major challenge in organic synthesis due to its challenging activation modes of multiple S-S bonds. The utilization of aryl di- and trithiosulfonates in nickel-catalyzed reductive coupling with aryl halides has been unexplored. Herein, we unprecedentedly describe PPh and Zn-collaborative reduction-induced nickel-catalytic selective C-S coupling of aryl di/trithiosulfonates with aryl halides to access sulfides over common disulfides or trisulfides.
View Article and Find Full Text PDFGeneration of thiyl radicals in a spatiotemporal controlled manner by light: Applied for the cis to trans isomerization of unsaturated fatty acids/phospholipids.
Redox Biol
February 2025
Department of Chemistry, Brown University, Providence, RI, 02912, USA. Electronic address:
Thiyl radicals are important reactive sulfur species and can cause cis to trans isomerization on unsaturated fatty acids. However, biocompatible strategies for the controlled generation of thiyl radicals are still lacking. In this work, we report the study of a series of naphthacyl-derived thioethers as photo-triggered thiyl radical precursors.
View Article and Find Full Text PDFHighly selective dual-signal readout HS probe: Applications in monitoring of water samples, food spoilage and live cell imaging.
Talanta
March 2025
School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan, 030006, China. Electronic address:
Article Synopsis
- - The new probe (DN) detects hydrogen sulfide (HS) using a chemical reaction that generates a noticeable color change from yellow to pink and produces red fluorescence in specific conditions.
- - DN shows excellent performance with a low detection limit of 15.1 nM and a quick response time of 5 minutes, making it effective for sensing HS.
- - A test kit using paper strips was created for checking meat freshness by detecting HS, and DN can also visualize HS in live cells, aiding research on its link to clinical diseases.
Want 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!