Monoallylation and monoalkylation of diketones and β-keto esters with allylic and benzylic alcohols catalysed by [Cp*Co(CHCN)][SbF] (I) are reported. The method does not require any additive and affords regioselective products. The mechanistic investigations were done by H NMR spectroscopy as well as control experiments. It has been shown that reactions proceed η-allyl complex formation or ally ether intermediate. The alkylation takes place only ether intermediate. The resulting allylated and alkylated products have been used for the synthesis of eleven new trisubstituted pyrazoles and one pyrazolone.
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http://dx.doi.org/10.1039/d0ra09778k | DOI Listing |
Org Lett
January 2025
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.
4'-Selective alkylation of nucleosides has been recognized as one of the ideal and straightforward approaches to chemically modified nucleosides, but such a transformation has been scarce and less explored. In this Letter, we combine a visible-light-mediated photoredox catalysis and hydrogen atom transfer (HAT) auxiliary to achieve β-C(sp)-H alkylation of alcohol on tetrahydrofurfuryl alcohol scaffolds and exploit it for 4'-selective alkylation of nucleosides. The reaction involves an intramolecular 1,5-HAT process and stereocontrolled Giese addition of the resultant radicals.
View Article and Find Full Text PDFChem Sci
December 2024
College of Materials Science and Engineering, Fuzhou University New Campus 350108 China
Atomically precise metal nanoclusters (NCs) have recently been recognized as an emerging sector of metal nanomaterials but suffer from light-induced poor stability, giving rise to the detrimental self-transformation into metal nanocrystals (NYs), losing the photosensitization effect and ultimately retarding their widespread applications in photoredox catalysis. Are metal NCs definitely superior to metal NYs in heterogeneous photocatalysis in terms of structural merits? To unlock this mystery, herein, we conceptually demonstrate how to rationally manipulate the instability of metal NCs to construct high-efficiency artificial photosystems and examine how the metal NYs self-transformed from metal NCs influence charge transfer in photoredox selective organic transformation. To our surprise, the results indicate that the Schottky-type electron-trapping ability of Au NYs surpasses the photosensitization effect of glutathione (GSH)-protected Au clusters [Au(GSH) NCs] in mediating charge separation and enhancing photoactivities towards selective photoreduction of aromatic nitro compounds to amino derivatives and photocatalytic oxidation of aromatic alcohols to aldehydes under visible light irradiation.
View Article and Find Full Text PDFBMC Chem
January 2025
The Affiliated Ganzhou Hospital, Jiangxi Medical College, Nanchang University, Ganzhou, 341000, Jiangxi, People's Republic of China.
Int J Mol Sci
December 2024
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China.
α-Hydroxy ketones are a crucial class of organic compounds prevalent in natural products and pharmaceutical molecules. The CO-promoted hydration of propargylic alcohols is an efficient method for the synthesis of α-hydroxy ketones. Herein, an ionic liquid (IL) was designed to catalyze this reaction individually under atmospheric CO pressure, volatile organic solvents, and additives.
View Article and Find Full Text PDFChem Sci
December 2024
LAQV@REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto Rua do Campo Alegre s/n 4169-007 Porto Portugal
The recently discovered metagenomic urethanases UMG-SP1, UMG-SP2, and UMG-SP3 have emerged as promising tools to establish a bio-based recycling approach for polyurethane (PU) waste. These enzymes are capable of hydrolyzing urethane bonds in low molecular weight dicarbamates as well as in thermoplastic PU and the amide bond in polyamide employing a Ser-Ser -Lys triad for catalysis, similar to members of the amidase signature protein superfamily. Understanding the catalytic mechanism of these urethanases is crucial for enhancing their enzymatic activity and improving PU bio-recycling processes.
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