The first example of rhodium-catalyzed nondirected C-H activation/annulation reactions for the construction of fused heterocyclic cations is reported herein with excellent regioselectivity. Deuterium-labeling experiments indicated that the C(sp)-H bond cleavage of the -methyl group might be the rate-limiting step during the reaction process. This protocol provides an opportunity to rapidly access highly π-conjugated fused heterocyclic cations, which opens up a new avenue for efficient screening of single-molecular white-light-emitting materials, pure red-light-emitting materials, and π-conjugated radical materials. Importantly, novel white-light-emitting materials exhibited distinct anti-Kasha dual-emission and could rapidly be fabricated into robust organic and low-cost white light-emitting diodes.
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http://dx.doi.org/10.1039/d4sc02188f | DOI Listing |
Chem Asian J
December 2024
National Institute of Pharmaceutical Education and Research, Medicinal Chemistry, Sector 67, 160062, S. A. S. Nagar, INDIA.
Ru(II)-Catalyzed "On Water" direct aryl C(sp2)-H amidation of 2-arylbenzo[d]-thiazole/oxazole with acyl azide is reported under silver-free condition. Deuterium scrambling experiments suggested reversible C-H activation catalyzed by active cationic ruthenium species. The organic solvents such as DCE, DMF, DMSO, MeCN, dioxane, and PhMe were not conducive for the C-H amidation except for PhCl in which case, however, inferior yield (31%) was obtained.
View Article and Find Full Text PDFInt J Mol Sci
November 2024
Research Institute of Chemistry, Peoples' Friendship University of Russia, 6 Miklukho-Maklaya Street, 117198 Moscow, Russia.
Herein, we describe a novel coupling between ambiphilic 2-pyridylselenyl reagents and nitriles featuring an active α-methylene group. Depending on the solvent employed, this reaction can yield two distinct types of cationic pyridinium-fused selenium-containing heterocycles, 1,3-selenazolium or 1,2,4-selenadiazolium salts, in high yields. This is in contrast to what we observed before for other nitriles.
View Article and Find Full Text PDFInt J Mol Sci
November 2024
Core Facility Center 'Arktika', Northern (Arctic) Federal University, Arkhangelsk 163002, Russia.
N,N'-Dialkylimidazolium-based ionic liquids are capable of completely dissolving lignocellulosic biomass at elevated temperatures and are considered as promising green solvents for future biorefining technologies. However, the obtained ionic liquid lignin preparations may contain up to several percent nitrogen. This indicates strong interactions between the biopolymer and the IL cation, the nature of which has not yet been clarified.
View Article and Find Full Text PDFBiomacromolecules
December 2024
School of Chemistry and the UNSW RNA Institute, UNSW Sydney, Sydney, NSW 2052, Australia.
Membraneless organelles, often referred to as condensates or coacervates, are liquid-liquid phase-separated systems formed between noncoding RNAs and intrinsically disordered proteins. While the importance of different amino acid residues in short peptide-based condensates has been investigated, the role of the individual nucleobases or the type of heterocyclic structures, the purine vs pyrimidine nucleobases, is less researched. The cell's crowded environment has been mimicked to demonstrate its ability to induce the formation of condensates, but more research in this area is required, especially with respect to RNA-facilitated phase separation and the properties of the crowding agent, poly(ethylene glycol) (PEG).
View Article and Find Full Text PDFOrg Biomol Chem
December 2024
Zhejiang Engineering Research Center of Fat-Soluble Vitamin, Shaoxing 312000, China.
The oxidative C2-C3 π bond activation strategy is the most efficient tool to synthesize oxygen-containing indoline, which frequently appears in natural products with various biological activities as structural units. Recently, the oxidation-induced cascade strategy through oxygenation activation of the indolic C2-C3 π bond of indoles has received much attention for its use in efficiently establishing complex indoline with oxygen-containing molecular architectures, and holds tremendous potential in the total synthesis of indole alkaloids. It can be carried out using potential activated indole radical cations or imine cation intermediates produced oxidative C2-C3 π bond activation of indole with various nucleophiles or ring-forming reagents by employing simple and non-decorated indoles as starting substrates.
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