The cross-coupling of aryl tosylates with amines and anilines was accomplished by using a Ni-based catalyst system from the combination of Ni(II)-(sigma-aryl) complexes/N-heterocyclic carbenes (NHCs). The feature, scope, and limitation of this reaction are disclosed.
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http://dx.doi.org/10.1021/jo7022558 | DOI Listing |
Org Biomol Chem
December 2024
Alexander Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya Str., 420008 Kazan, Russia.
Efficient catalytic systems for various organic transformations in green solvents, especially water, are in great demand. Catalytically active bis-NHC complexes of palladium(II) based on imidazole-4,5-dicarboxylic acid with different lipophilicities were obtained. The synthesis of imidazolium salts was complicated by the formation of side products of nucleophilic substitution by iodide ions in the Menshutkin reaction involving alkyl iodides, which was successfully resolved by using alkyl tosylates.
View Article and Find Full Text PDFChemistry
December 2024
Albert-Ludwigs-Universität Freiburg, Institute of Organic Chemistry, Albertstraße 21, 79104, Freiburg, Germany.
A (3+3)-cycloaddition to afford 2-azabiyclo[3.1.1]heptanes was realized by reacting highly strained aryl bicyclo[1.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Key Laboratory of Organic Synthesis of Jiangsu Province, MOE Key Laboratory of Geriatric Diseases and Immunology, Suzhou Key Laboratory of Pathogen Bioscience and Anti-infective Medicine, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123, Suzhou, China.
A palladium-catalyzed highly C-S-selective Stille cross-coupling between aryl thianthrenium salts and tri- or tetrasubstituted alkenyl stannanes is described. Herein, critical challenges including site- and chemoselectivity control are well addressed through C-H thianthrenation and C-S alkenylation, thereby providing an expedient access to stereodefined tri- and tetrasubstituted alkenes in a stereoretentive fashion. Indeed, the palladium-catalyzed Stille-alkenylation of poly(pseudo)halogenated arenes displays privileged capability to differentiate C-S over C-I, C-Br, C-Cl bonds, as well as oxygen-based triflates (C-OTf), tosylates (C-OTs), carbamates and sulfamates under mild reaction conditions.
View Article and Find Full Text PDFOrg Lett
June 2024
College of Pharmaceutical Sciences, Ritsumeikan University, Kusatsu 525-8577, Shiga, Japan.
α-Fluorinated aryl esters pose a challenge in synthesis via -arylation of α-fluorinated carboxylates owing to their low reactivities. This limitation has been addressed by combining a silver catalyst with aryl(trimethoxyphenyl)iodonium tosylates to access α-fluorinated aryl esters. We envision that the catalytic system involves high-valent aryl silver species generated via the oxidation of silver(I) salt.
View Article and Find Full Text PDFJ Org Chem
June 2024
School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, P. R. China.
The nucleophilic ring-opening of aziridine derivatives provides an important synthetic tool for the preparation of various β-functionalized amines. Amines as nucleophiles are employed to prepare synthetically useful 1,2-diamines in the presence of various catalysts or activators. Herein, the B(OH)-mediated reductive ring-opening transformation of -tosyl aziridines by nitroarenes was developed.
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