Herein we report the site-selective silylation of the ribonucelosides. The method enables a simple and efficient procedure for accessing suitably protected monomers for automated RNA synthesis. Switching to the opposite enantiomer of the catalyst allows for the selective silylation of the 3'-hydroxyl, which could be used in the synthesis of unnatural RNA or for the analoging of ribonucelosides. Lastly, the procedure was extended to ribavirin a potent antiviral therapeutic.
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http://dx.doi.org/10.1021/ol402023c | DOI Listing |
Macromolecules
November 2024
Materials Department, University of California, Santa Barbara, Santa Barbara, California 93106, United States.
Silicone bottlebrush copolymers and networks derived from cyclic carbosiloxanes are reported and shown to have enhanced properties and recyclability compared with traditional dimethylsiloxane-based materials. The preparation of these materials is enabled by the synthesis of well-defined heterotelechelic macromonomers with Si-H and norbornene chain ends via anionic ring-opening polymerization of the hybrid carbosiloxane monomer 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane. These novel heterotelechelic α-Si-H/ω-norbornene macromonomers undergo efficient ring-opening metathesis copolymerization to yield functional bottlebrush polymers with accurate control over molecular weight and functional-group density.
View Article and Find Full Text PDFAnal Chim Acta
December 2024
Grupo de Investigación en Cromatografía y Técnicas Afines GICTA, Departamento de Química, Facultad de Ciencias Exactas y Naturales, Universidad de Caldas, Calle 65 # 26-10, Manizales, 170004, Colombia. Electronic address:
Org Lett
November 2024
Universite Claude Bernard Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR 5246 du CNRS. 1, rue Victor Grignard, 69100 Villeurbanne, France.
We report a dual Ni/photoredox-catalyzed cross-coupling method for propargyl carbonates and nonactivated alkyl bromides, facilitating the synthesis of a variety of substituted allenes under mild and practical conditions. Mechanistically, the reaction integrates Ni-catalyzed activation of the propargyl electrophile via S' oxidative addition at Ni(I) with silyl radical-induced activation of the alkyl halide through halogen-atom transfer. This methodology provides a gentle approach for introducing allenyl groups into complex halogenated aliphatic molecules, offering further opportunities for derivatization.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R., China.
Despite recent advances in cluster-based catalysis for organic synthesis, the substrate scope of reactions catalyzed by metal nanoclusters is typically not superior to previously established catalytic systems. Herein, we develop new atomically precise copper nanoclusters for protosilylation, with scope expanding to alkenes and simple enynes that were not suitable for prior synthetic methodologies with traditional copper complexes. The involvement of a second copper center in the metal kernel during the migratory insertion step is thought to be responsible for the expanded scope.
View Article and Find Full Text PDFJ Hazard Mater
December 2024
Department of Civil and Environmental Engineering, University of Wisconsin-Milwaukee, Milwaukee, WI 53201, United States. Electronic address:
Organically modified clays (organoclays) have been considered effective adsorbents for the treatment of per- and polyfluoroalkyl substances (PFAS). However, the stability of organoclays prepared through the conventional cation exchange approach has been a major concern for their practical application. In this study, we reported the development of a new organically functionalized clay by grafting pillared clay substrate with an organosilane through covalent bonding.
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