Cobalt(III)-catalyzed thiocarbamate directed aminocarbonylation and amination of C-H bonds are described to access diverse amides. Biologically relevant pyrrolo[1,2-]imidazoles were readily accessed one-pot intramolecular cyclization at the thiocarbamoyl directing group. Notably, C-N amidation proceeded smoothly with an elusive catalyst TON of 250 for this Cp*Co(III)-catalysis. Broad scope, scalability, and easy removal of DG are other key features of these methods. The mechanisms of these C-H amidation reactions were proposed through control experiments and DFT calculations.
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http://dx.doi.org/10.1039/d2cc03992c | DOI Listing |
Chempluschem
December 2024
Budapest University of Technology and Economics, Department of Chemical and Environmental Process Engineering, Muegyetem rkp. 3., 1111, Budapest, HUNGARY.
The palladium-catalyzed aminocarbonylation is one of the most effective methods for the synthesis of carboxamides having great importance. Replacing fossil-based organic solvents in this routinely used catalytic protocol with biomass-derived media is crucial for developing environmentally safe alternatives and towards sustainability considerations. In this study, the open-chain derivatives of bio-originated substance g-valerolactone i.
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November 2024
Department of General and Inorganic Chemistry, University of Pécs, Ifjúság u. 6., H-7624 Pécs, Hungary.
Palladium-catalyzed carbonylation reactions of -phenylene dihalides were studied using aminoethanols as heterobifunctional ,-nucleophiles. The activity of aryl-iodide and -bromide as well as the chemoselective transformation of amine and hydroxyl functionalities were studied systematically under carbonylation conditions. Aminocarbonylation can be selectively realized under optimized conditions, enabling the formation of amide alcohols, and the challenging alkoxycarbonylation can also be proved feasible, enabling amide-ester production.
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October 2024
Research Group of Organic Synthesis and Catalysis, University of Pannonia, Egyetem u. 10, 8200 Veszprém, Hungary.
Imidazo[1,2-]pyridines and especially their amide derivatives exhibit a wide range of favourable pharmacological properties. In this work, Pd-catalysed carbonylation was used for the first time for the introduction of the carboxamide moiety into positions 6 or 8. A recyclable Pd catalyst, with palladium immobilised on a supported ionic liquid phase decorated with pyridinium ions, was used efficiently for the conversion of 6- or 8-iodo derivatives to the products.
View Article and Find Full Text PDFOrg Lett
October 2024
Faculdade de Ciências Farmacêuticas, Departamento de Farmácia, Universidade de São Paulo, São Paulo, SP 05508-220, Brazil.
Cascade reactions are important synthetic tools for the synthesis of heterocyclic molecules, particularly those catalyzed by palladium. Herein, we report a palladium-catalyzed aminocarbonylative cyclization of new 1-alkynyl-2-iodo-d-glucals, which undergo a tandem carbonylative cyclization in the presence of various amine nucleophiles. A broad range of aromatic and aliphatic amines were applied as coupling partners, resulting in the selective and high-yield synthesis of glycosides fused to pyridinones.
View Article and Find Full Text PDFInt J Mol Sci
September 2024
HUN-REN-PTE Research Group for Selective Chemical Syntheses, Ifjúság útja 6., H-7624 Pécs, Hungary.
A library of C-3 functionalized flavones was successfully provided via palladium-catalyzed amino- and aryloxycarbonylation reactions of 3-iodoflavone (), under mild conditions. This methodology showed good functional group tolerance using a variety of amines and phenols, under an atmospheric pressure of carbon monoxide as a carbonyl source. While the flavone-3-carboxamides () were produced in 22-79%, the flavone-3-carboxylates () were obtained in excellent yields (up to 88%), under identical reaction conditions, just by switching -nucleophiles to -nucleophiles.
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