We report the synthesis and characterization of a variety of trans-3,4-substituted cyclopentanones and the corresponding tosylhydrazone derivatives starting with diethyl fumarate. Protection of the keto group followed by selective monohydrolysis of esters was achieved, resulting in cyclopentanones with different substituents at positions 3 and 4. The tosylhydrazone derivative of each cyclopentanone intermediate was prepared in moderate to good yields. These compounds are potential precursors for functionalized methanofullerenes.
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http://dx.doi.org/10.3390/molecules17010001 | DOI Listing |
J Org Chem
January 2025
College of Chemistry and Environmental Science, Qujing Normal University, Qujing, Yunnan 655011, China.
A novel metal- and azide-free methodology for the synthesis of trifluoromethylated 1,2,3-triazoles from arylamines with a new 3-bromo-1,1,1-trifluoropropan-2-one derived tosylhydrazone has been developed under mild reaction conditions. The new α-bromo-trifluoromethylated tosylhydrazone reagent was operationally safe and bench-stable from low-cost and readily commercially available starting materials in the iodine-promoted aerobic oxidative cycloaddition reaction with arylamines, affording a variety of trifluoromethylated 1,2,3-triazoles in good to excellent yields.
View Article and Find Full Text PDFNat Commun
December 2024
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan, 410081, China.
Owning to the versatile nature in participation of Diels-Alder (D-A) reactions, the development of efficient approaches to generate active ortho-quinodimethanes (o-QDMs) has gained much attention. However, a catalytic method involving coupling of two readily accessible components to construct o-QDMs is lacking. Herein, we describe a palladium carbene migratory insertion enabled dearomative C(sp)-H activation to form active o-QDM species through the cross-coupling of N-tosylhydrazones with aryl halides.
View Article and Find Full Text PDFChem Sci
November 2024
Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica "Enrique Moles", Instituto de Investigación Sanitaria del Principado de Asturias (ISPA), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Oviedo C/ Julián Clavería 8 33006 Oviedo Spain
The reactions of cyclic α,β-unsaturated -tosylhydrazones and alkylboronic acids promoted by 370-390 nm light in the presence of a base give rise to allylic boronic acids that can be trapped as the corresponding pinacolboronates by treatment with pinacol. This reaction features wide scope regarding both coupling partners and functional group tolerance, allowing for the incorporation of a variety of natural product-derived fragments. The allylic boronic acids can be also reacted in a one-pot process with aldehydes, to produce homoallylic alcohols with very high diastereoselectivity.
View Article and Find Full Text PDFOrg Biomol Chem
November 2024
College of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, People's Republic of China.
A palladium-catalyzed cascade reaction of α,β-unsaturated -tosylhydrazones with iodoarene derivatives containing a nucleophilic group has been developed, which provides facile access to 2-chromenes and 2-quinolines, respectively. Additionally, the double Pd-carbene migratory insertion/nucleophilic substitution processes for the synthesis of a ternary heterocyclic skeleton were possible in the developed catalytic system.
View Article and Find Full Text PDFJ Org Chem
July 2024
Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.
We report herein an expedient method for the regioselective synthesis of indoles from -haloanilines and α-ketol-derived -tosylhydrazones. This two-step, modular synthesis of -H indoles can be carried out conveniently without purification of intermediates.
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