Photolysis of S,C-sulfonium ylides derived from thioanisol, thiophene, benzothiophene, or dibenzothiophene provides products deriving from dicarbomethoxycarbene. In methanol, no rearrangement of the carbene to the ketene derivative is observed. Formation of dibenzothiophene and benzothiophene is quantitative. For the thiophene-based ylide, insertion of the carbene into the alpha-CH bond of thiophene is observed. Evidence is presented that supports formation of both singlet and triplet carbene.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ja076351w | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Ph3PC - A Monosubstituted C(0) Atom in Its Triplet State.
Angew Chem Int Ed Engl
January 2025
TU Dortmund: Technische Universitat Dortmund, Fakultät für Chemie und Chemische Biologie, Otto-Hahn Str.6, 44227, Dortmund, GERMANY.
This study introduces a novel class of carbon-centered diradicals: a monosubstituted C-atom stabilized by a phosphine. The diradical Ph3P→C was photochemically generated from a diazophosphorus ylide precursor (Ph3PCN2) and characterized by EPR and isotope-sensitive ENDOR spectroscopy at low temperatures. Ph3P→C features an axial zero-field splitting parameter D = 0.
View Article and Find Full Text PDFReactivity of Anomalous Aziridines for Versatile Access to High Fsp Amine Chemical Space.
Acc Chem Res
January 2025
Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706, United States.
ConspectusThe manipulation of strained rings is a powerful strategy for accessing the valuable chemical frameworks present in natural products and active pharmaceutical ingredients. Aziridines, the smallest N-containing heterocycles, have long served as building blocks for constructing more complex amine-containing scaffolds. Traditionally, the reactivity of typical aziridines has been focused on ring-opening by nucleophiles or the formation of 1,3-dipoles.
View Article and Find Full Text PDFCu(II)-Catalyzed Annulative Sulfonylimination of α-Carbonyl-γ-alkynyl Sulfoxonium Ylides through Sulfoxonium Ylide Elimination for Access to ()-1-Isochromenes.
J Org Chem
January 2025
School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou 221116, China.
1-Isochromene scaffolds are ubiquitous in natural products and significant bioactive molecules. Although several methods for these molecular syntheses have been developed, reports on the efficient construction of iminated isochromenes are still rather limited. Herein, we report a new Cu(II)-catalyzed annulation and sulfonylimination cascade of α-carbonyl-γ-alkynyl sulfoxonium ylides with sulfamides, enabling direct C-C σ-bond elimination to furnish iminated ()-1-isochromenes in 51-97% yields.
View Article and Find Full Text PDFPushing the limits of electron donation for -chelating ligands an alliance of phosphonium ylide and anionic abnormal NHC.
Chem Commun (Camb)
January 2025
LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France.
The grafting of a -(CH)PR moiety on an NHC ligand backbone in the Mn(I) complex [Cp(CO)Mn(IMes)] followed by double deprotonation opens a route to bidentate ligands with extreme electron-donating character. Such remarkable electronic properties can even allow intramolecular sp C-H functionalization in typically inert square-planar Rh(I) dicarbonyl complexes.
View Article and Find Full Text PDFUnlocking the potential of azide-phosphine Staudinger reaction for the synthesis of poly(arylene iminophosphorane)s and materials therefrom.
Commun Chem
January 2025
National Institute of Chemistry, Hajdrihova 19, SI-1001, Ljubljana, Slovenia.
Iminophosphoranes with the general formula (RP═NR') have great potential in synthetic chemistry as valuable precursors/intermediates in organic synthesis or as building blocks for various organic compounds. However, the synthetic approaches and conditions to prepare iminophosphoranes are still poorly understood, limiting the utility of this chemistry for organic materials. In this article, a simple and efficient synthesis of previously unattainable poly(arylene iminophosphoranes) is reported.
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!