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A series of β-ketoenamines was synthesized from various phenacyl sulfoxides bearing 1-methyl-1-tetrazole and oximes in moderate to excellent yields. The proposed mechanism involved the generation of α-sulfines from sulfoxides through thermolytic elimination, regiospecific formal [3 + 2] annulations, and elimination of SO. This protocol provides convenient access to a variety of synthetically valuable -unprotected β-enaminones with absolute selectivity.
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http://dx.doi.org/10.1021/acs.joc.3c02717 | DOI Listing |
Chem Commun (Camb)
September 2025
Department of Organic Synthesis and Process Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad 500007, India.
A CFOH-catalysed tandem cyclization of -alkynylnaphthols and -quinone monoketals is disclosed. The CFOH catalyst activates alkynylnaphthol to generate an all-carbon tetrasubstituted VQM by nucleophilic addition to quinone monoketal (Michael addition). Furthermore, the CFOH catalyst triggers -quinone monoketal to generate an electrophilic oxocarbenium cation to be captured by -alkynylnaphthol regiospecifically, resulting in the formation of an all-carbon tetrasubstituted VQM, followed by an intramolecular cyclization to afford a series of 1-(3-arylbenzofuran-2-yl)naphthalen-2-ols.
View Article and Find Full Text PDFJ Org Chem
May 2025
Department of Chemistry and Biomolecular Science, Gifu University, 1-1, Yanagido, Gifu 501-1193, Japan.
Planar tricyclic aromatics and azaheteroaromatics are of significant interest to organic chemists in the field of materials science owing to their excellent photoconductivity, electroluminescence and fluorescence properties enabled by their rigid extended π-conjugation. Furthermore, tricyclic azaheteroaromatics are effective ligands for organometallic catalysis and a prominent drug discovery framework. Herein, we present the first one-step synthesis of a less-accessible tricyclic fluorophore comprising a 5,6-difluoro-2,9-diarylpyrimido[5,4-]quinazoline core entailing the regiospecific tandem condensation of tetrafluoroterephthalonitrile and derivatives of benzamidine hydrochloride in the presence of potassium carbonate or cesium carbonate under mild conditions.
View Article and Find Full Text PDFAnal Chem
April 2025
School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia.
[2 + 2] Photocycloaddition reactions are powerful tools for synthetic chemistry. However, analysis of the head-to-head or head-to-tail conformation of the resulting cycloadducts is often challenging by conventional spectroscopic methods. Herein, we report the analysis of coumarin and styrylpyrene cycloadducts by cyclic ion-mobility tandem mass spectrometry (cIM-MS/MS) to characterize the regioisomeric products of this important class of photoresponsive groups.
View Article and Find Full Text PDFFood Res Int
February 2025
Food Sciences, Department of Life Technologies, Faculty of Technology, University of Turku FI-20014 Turku, Finland.
Triacylglycerols (TGs) are the primary lipids of plant oils and the positional distribution of fatty acids (FAs) is essential to physicochemical, functional, and nutritional qualities of oils. Most studies have reported TG species in plant oils. In some studies, FA combinations in each TG species have been reported still neglecting the regioisomer composition of TGs.
View Article and Find Full Text PDFJ Org Chem
November 2024
School of Chemistry, Indian Institute of Science Education and Research, Thiruvananthapuram, Kerala 695551, India.
This study demonstrates the direct conversion of vinylogous esters into selectively protected 6-acyl resorcinols (4-alkoxy/aryloxy-2-hydroxy arylketones) in a regiospecific manner. Resorcinyl ketones are first-time synthesized, diverging from their traditional roots, originating from non-benzenoid pool materials. Converting cyclohexenones into phenol- or resorcinol-based arylketones remains challenging due to the stability and reactivity issues of intermediate products.
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