Lanthanide derivatives comprising arylhydrazones of beta-diketones: cooperative E/Z isomerization and catalytic activity in nitroaldol reaction

作者：Mahmudov Kamran T^*; Guedes da Silva M Fatima C; Sutradhar Manas; Kopylovich Maximilian N; Huseynov Fatali E; Shamilov Nazim T; Voronina Anna A; Buslaeva Tatyana M; Pombeiro Armando J L

来源：Dalton Transactions, 2015, 44(12): 5602-5610.

DOI：10.1039/c4dt03788j

Two complexes [KLa(HL1)(2){(CH3)(2)NCHO}(2)(H2O)(3)] (1) and [Sm(H2O)(9)](E-H2L2)(3)center dot 2H(2)O (2) were synthesized by the reaction of lanthanum(III) and samarium(III) nitrates with potassium 3-(2-(2,4-dioxopentan-3-ylidene) hydrazinyl)-2-hydroxy-5-nitrobenzenesulfonate (KH2L1) and potassium (E, Z)-5-chloro-3-(2-(1,3-dioxo-1-phenylbutan-2-ylidene)hydrazinyl)-2-hydroxybenzenesulfonate (KH2L2), respectively. Both complexes were fully characterized by elemental analysis, IR, H-1 and C-13 NMR spectroscopy, ESI-MS and single-crystal X-ray diffraction. Cooperative E, Z. E isomerization of KH2L2, induced by resonance assisted hydrogen bonding and ionic interactions, occurs upon the interaction with Sm(III). Catalytic activities of KH2L1,2 and their lanthanide derivatives were evaluated in the Henry reaction of nitroethane with a variety of aromatic and aliphatic aldehydes. Good yields (up to 91%) and diastereoselectivities (syn/anti 3 : 1) were observed in the reactions catalyzed by 1 in water.

• 出版日期2015