An efficient approach to meso-unsubstituted β-silylporphyrins was developed through highly regioselective Ir-catalyzed C-H activation, in the presence of HSiMe(OSiMe) as the Si source, from meso-unsubstituted porphyrins. Further transformations of the silyl group, such as oxidation, halogenation, and cross-coupling reactions, could be achieved under mild conditions, demonstrating the synthetic utility of β-silylporphyrins as a multipurpose synthon for fabricating porphyrin derivatives.
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http://dx.doi.org/10.1039/c6ob02243j | DOI Listing |
Org Biomol Chem
January 2025
Institute of Natural Sciences and Mathematics, Ural Federal University, 51 Lenina Ave., 620000 Ekaterinburg, Russian Federation.
The labile tautomerism of -unsubstituted 5-acyl-4-pyridones, which exist in the form of 4-pyridone or 4-hydroxypyridine depending on the solvent, has been demonstrated. This equilibrium determines the reactivity of pyridones and their ability to undergo substitution reactions of the OH group. A regioselective and convenient method for the construction of functionalized pyrazolo[4,3-]pyridines (30-93%) based on the intramolecular amination reaction of 4-pyridones with hydrazines has been developed.
View Article and Find Full Text PDFJ Org Chem
January 2025
Département de Chimie, 1045 av. De la Médecine, Université Laval, Québec City, Quebec G1 V 0A6, Canada.
In this work, we developed a site-selective functionalization of levoglucosan analogues. This strategy used simple zinc diamine complexes for regioselective functionalization at O2 or O4. Successful transformations of monotosyl analogues allowed the preparation of useful intermediates in carbohydrate chemistry, such as four protected Černý epoxides and three protected amino sugars.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Department of Chemistry, Institute of Technology Delhi, Hauz Khas, New Delhi 110-016, India.
Pyridinium salts are amine surrogates that are abundant in nature and the redox active nature of the pyridinium salts allows them to serve as precursors for generating radical species under mild conditions that can be initiated by light, heat or metal catalysis. The stereoselective formation of products has always been a topic of interest for synthetic chemists worldwide. In this context, pyridinium salts can readily undergo single electron reduction to form a neutral radical, and the N-X bond's subsequent fragmentation furnishes the X radical without any harsh reaction conditions.
View Article and Find Full Text PDFAdv Mater
January 2025
Department of Materials Science and Engineering, Massachusetts Institute of Technology (MIT), 77 Massachusetts Avenue, Cambridge, MA, 02139, USA.
Polymer-brush-grafted nanoparticles (PGNPs) that can be covalently crosslinked post-processing enable the fabrication of mechanically robust and chemically stable polymer nanocomposites with high inorganic filler content. Modifying PGNP brushes to append UV-activated crosslinkers along the polymer chains would permit a modular crosslinking strategy applicable to a diverse range of nanocomposite compositions. Further, light-activated crosslinking reactions enable spatial control of crosslink density to program intentionally inhomogeneous mechanical responses.
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