1294518-07-2Relevant academic research and scientific papers
Unexpectedly efficient activation of push-pull nitriles by a Pt II center toward dipolar cycloaddition of Z-nitrones
Kritchenkov, Andreii S.,Bokach, Nadezhda A.,Haukka, Matti,Kukushkin, Vadim Yu.
, p. 4175 - 4182 (2011)
PtII-coordinated NCNR′2 species are so highly activated towards 1,3-dipolar cycloaddition (DCA) that they react smoothly with the acyclic nitrones ArCHN+(O-)R′′ (Ar/R′′ = C6H4Me-p/Me; C6H 4OMe-p/CH2Ph) in the Z-form. Competitive reactivity study of DCA between trans-[PtCl2(NCR)2] (R = Ph and NR′2) species and the acyclic nitrone 4-MeC6H 4CHN+(O-)Me demonstrates comparable reactivity of the coordinated NCPh and NCNR′2, while alkylnitrile ligands do not react with the dipole. The reaction between trans-[PtCl 2(NCNR′2)2] (R′2 = Me2, Et2, C5H10) and the nitrones proceed as consecutive two-step intermolecular cycloaddition to give mono-(1a-d) and bis-2,3-dihydro-1,2,4-oxadiazole (2a-d) complexes (Ar/R′′ = p-tol/Me: R′2 = Me2a, R′2 = Et 2b, R′2 = C5H10c; Ar/R′′ = p-MeOC6H4/CH2Ph: R′2 = Me2d). All complexes were characterized by elemental analyses (C, H, N), high resolution ESI-MS, IR, 1H and 13C{1H} NMR spectroscopy. The structures of trans-1b, trans-2a, trans-2c, and trans-2d were determined by single-crystal X-ray diffraction. Metal-free 5-NR′2-2,3-dihydro-1,2,4-oxadiazoles 3a-3d were liberated from the corresponding (dihydrooxadiazole) 2PtII complexes by treatment with excess NaCN and the heterocycles were characterized by high resolution ESI+-MS, 1H and 13C{1H} spectroscopy.
