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Palladium-catalyzed and ligand-controlled cycloaddition of ()-β-trifluoromethylated enones has been described, providing powerful synthetic strategies for two α-CF-substituted O-heterocycles, tetrahydro-2-pyrans and 5-oxaspiro[2.4]heptanes. The readily available substrates bearing various functional groups have shown variable product chemoselectivities. The salient features also included novel products with potential values and diverse derivatizations. The mechanistic investigations revealed the stereochemistry of the O-heterocyclic products.
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http://dx.doi.org/10.1021/acs.joc.5c01706 | DOI Listing |
J Org Chem
September 2025
School of Pharmacy, Changzhou University, Changzhou, Jiangsu Province 213164, China.
Palladium-catalyzed and ligand-controlled cycloaddition of ()-β-trifluoromethylated enones has been described, providing powerful synthetic strategies for two α-CF-substituted O-heterocycles, tetrahydro-2-pyrans and 5-oxaspiro[2.4]heptanes. The readily available substrates bearing various functional groups have shown variable product chemoselectivities.
View Article and Find Full Text PDFJ Phys Chem A
June 2025
Srinivasa Ramanujan Institute for Basic Sciences (SRIBS), Pampady, Kottayam 686501, India.
The phenomenon of positive cooperativity in noncovalent complexes, arising from electron donor-acceptor (eDA) interactions and subsequent electron reorganization, has been investigated by using density functional theory (DFT) at the ωB97XD/6-311 + G(3df,2pd) level. The study focuses on the interaction of various nitrogen- and oxygen-containing heterocycles with HF and HCl molecules. The formation of dimer complexes leads to electron flow from the nitrogen lone pair to the hydrogen halide, enhancing the electron density on the halogen atom, as made evident by molecular electrostatic potential (MESP) analysis.
View Article and Find Full Text PDFNat Commun
April 2025
Faculty of Chemistry and Life Sciences, Changchun University of Technology, 2055 Yan'An Street, Changchun, Jilin, 130012, P. R. China.
Since its advent 120 years ago, the [2+n] coupling cyclization of ketene has been prevalently used for the synthesis of N- and O-heterocycles. In contrast, its vinylogous version, i.e.
View Article and Find Full Text PDFUltrason Sonochem
July 2025
Department of Drug Science and Technology, University of Turin, Via P. Giuria 9, 10125 Turin, Italy.
Xanthenes are an important class of heterocycles in medicinal chemistry due to their diverse pharmacological properties. These tricyclic aromatic compounds, characterised by a dibenzo[b,e]pyran core with an oxygen atom at their central position, have gained significant attention for their extensive applications. Beyond pharmaceuticals, xanthenes are widely used in textiles, food industries, electro-optical devices, dyes, and bioimaging agents.
View Article and Find Full Text PDFNat Commun
April 2025
School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, China.
Inherently chiral calix[4]arenes represent a distinct class of chiral frameworks whose chirality arises from the dissymmetry of the entire molecule. Although these chiral scaffolds have been widely applied in various research fields, their catalytic enantioselective synthesis remains largely underexplored. Herein, we report the enantioselective synthesis of inherently chiral calix[4]arenes using an organocatalyzed desymmetrization method.
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