[reaction: see text] Olefinic sulfamates derived from primary and secondary alcohols undergo intramolecular copper-catalyzed aziridination in the presence of iodosylbenzene to afford novel bicyclic fused aziridines. The latter were opened by various nucleophiles to give the corresponding substituted cyclic sulfamates, which in turn reacted, after nitrogen activation, with a second nucleophile at the carbon atom bearing the oxygen atom. Concomitant removal of the sulfonyloxy moiety thus gave access to polysubstituted amines.
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http://dx.doi.org/10.1021/ol0200899 | DOI Listing |
Chem Commun (Camb)
October 2024
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781039, India.
Copper(I)-catalyzed (4+3)-cycloaddition of 4-indolylcarbinols with aziridines has been accomplished to furnish azepinoindoles. The chirality transfer, substrate scope, functional group tolerance, natural product modification and tandem C-C/C-N bond formation are the important practical features.
View Article and Find Full Text PDFOrg Biomol Chem
August 2024
Department of Chemistry, National Institute of Technology Karnataka, Surathkal, Mangalore, 575025, India.
A copper-catalyzed aerobic [3 + 2] annulation reaction to access various pyrazole-bound chalcones starting from readily available and cost-effective hydrazones and dienones is reported. These pyrazole-bound chalcones were further utilized effectively to prepare a series of pyrazole-linked hybrid molecules, such as pyrazole-pyrazoline, pyrazole-aziridine, and pyrazole-pyridine hybrids by efficient simple transformations. Synthetically challenging hybrid molecules were obtained in a simple, two-step process with high atom economy under aerobic copper catalysis.
View Article and Find Full Text PDFOrg Lett
December 2023
School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, Shandong 273165, People's Republic of China.
A Cu-catalyzed coupling of cyclic imino esters with 2-azirines has been developed to synthesize novel optically active aziridines in high yields with excellent levels of diastereo- and enantioselectivities under mild conditions. This novel protocol features a broad substrate scope and good functional group compatibility, and it enriches the existing reaction type of rapid synthesis of optically active aziridines bearing vicinal tetrasubstituted stereogenic carbon centers.
View Article and Find Full Text PDFFront Chem
September 2023
Department of Chemistry, School of Science, Kwansei Gakuin University, Sanda, Japan.
Herein we report a copper-catalyzed synthesis of imidazolidine by employing the reaction of aziridine with imine. The reaction smoothly provided a diverse range of 2-substituted imidazolidines with high compatibility with various functional groups. Moreover, during our investigation, we discovered that isocyanate also reacted with aziridine to yield substituted imidazolidinones efficiently.
View Article and Find Full Text PDFACS Catal
January 2023
Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, 21007 Huelva, Spain.
In the context of copper-catalyzed nitrene transfer to olefins, many systems operate upon mixing a CuX salt (X = halide, OTf) and a polydentate N-based ligand, assuming that the X ligand is displaced from the coordination sphere toward a counterion position. Herein, we demonstrated that such general assumption should be in doubt since studies carried out with the well-defined copper(I) complexes (TTM)CuCl and [(TTM)Cu(NCMe)]PF (TTM = tris(triazolyl)methane ligand) demonstrate a dual behavior from a catalytic and mechanistic point of view that exclusively depends on the presence or absence of the chloride ligand bonded to the metal center. When coordinated, the turnover-limiting step corresponds to the formation of the carbon-nitrene bond, whereas in its absence, the highest barrier corresponds to the formation of the copper-nitrene intermediate.
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