A new method for the synthesis of dihydroimidazo[1,2-a][1,3,5]triazin-4(6H)-ones via copper(I)-catalyzed hydroamination was developed. In addition, for the first time, iodoalkynes were shown to participate in the copper(I)-catalyzed intramolecular hydroamination reaction with exclusive formation of E-isomers.
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http://dx.doi.org/10.1021/jo1016376 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Freie Universitat Berlin, Chemistry and Biochemistry, Fabeckstraße 34-36, 14195, Berlin, GERMANY.
Neutral mesoionic carbenes (MICs) based on a 1,2,3-triazole core have had a strong impact on various branches of chemistry such as homogeneous catalysis, electrocatalysis, and photochemistry/photophysics. We present here the first general synthesis of anionic mesoionic carbenes (anMICs) based on a 1,2,3-triazole core and a borate backbone. The free anMIC is stable in solution under an inert atmosphere at low temperatures, and can be stored for several weeks.
View Article and Find Full Text PDFJ Org Chem
January 2025
School of Chemistry, IGCME, The Key Laboratory of Low-Carbon Chemistry & Energy Conservation of Guangdong Province, Guangdong Provincial Key Laboratory of Chiral Molecules and Drug Discovery, Sun Yat-sen University, Guangzhou 510006, People's Republic of China.
The ligand-free Lewis acid-mediated regioselective hydroamination and hydroarylation of styrenes have been successfully developed in the presence of isatins or heterocyclic aryl compounds such as benzothiophenes and benzofurans. The reactions tolerate a variety of functional groups and afford the corresponding products in moderate to good yields. Deuterium labeling experiments show that the functionalized hydrogen of styrenes was derived from the nitrogen-hydrogen of the substrates in the hydroamination.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology (ECUST), Shanghai 200237, China.
A highly efficient base-controlled synthesis of -β-trifluoromethyl-substituted 2-benzo[]imidazole-2-thiones and 2-fluoro-4-benzo[4,5]imidazo[2,1-][1,3]thiazines hydroamination or defluorinative cyclizations of α-(trifluoromethyl)styrenes with 2-mercaptobenzimidazole was developed.
View Article and Find Full Text PDFOrg Biomol Chem
December 2024
School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, P. R. China.
Herein, we report a novel Al compound supported by a NacNac ligand that facilitates the anti-Markovnikov hydroamination of aromatic alkenes and primary amines. This represents the first instance of an aluminum-catalyzed intermolecular hydroamination of alkenes, successfully synthesizing a variety of aromatic imine derivatives. The proposed mechanism suggests that the coordination activation of BuOK by ether solvents is crucial, allowing the BuO anion to coordinate with the catalyst's Al center, thus forming a key intermediate.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States.
An acid-promoted dearomative rearrangement of -arylhydroxylamines affords 2-aminocyclohexadien-1-ones, which can in turn be reductively quenched for the synthesis of -aminoalcohols on a cyclohexadiene core. This method serves as an efficient entry to the pharmaceutically relevant 1-arylcyclohexylamine scaffold in two steps (one purification) from commercially available or readily prepared 2-arylphenols.
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