Synthesis, crystal structure and catalytic properties in the diastereoselective nitroaldol (Henry) reaction of new zinc(II) and cadmium(II) compounds

• Published in: Polyhedron Vol. 158; pp. 71 - 75
• Main Authors: Jlassi, Raja, Khalladi, Ahmed, Naïli, Houcine, Rüffer, Tobias, Lang, Heinrich, Rekik, Walid
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 15.01.2019; Elsevier
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Crystal structure; Crystallography; Diastereoselectivity; Henry reaction; Hybrid materials; Physical Sciences; Science & Technology; Supramolecular chemistry; Hybrid materials; Diastereoselectivity; Supramolecular chemistry; Crystal structure; Henry reaction; DESIGN; NITRATE; LIGANDS; CU(II); COMPLEXES; SPECTRA; DOUBLE SULFATES
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2018.10.064

Both the 0D coordination complex [Zn(im)4](NO3)2] (1) and 1D coordination polymer [CdNa2(µ-L2)]n·6.34H2O (2), where (L) is (2-(2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl)terephthalate), have been successfully synthesized and characterized by IR and UV–Vis absorption spectroscopies and single-crystal X-ray diffraction. Furthermore, 1 and 2 were used as catalysts in the Henry reaction with nitroethane and aldehydes. The diastereoselectivities of the products were determined using 1H NMR spectroscopy. [Display omitted] The new complex [Zn(im)4](NO3)2 (1) was synthesized and crystallographically characterized. In the solid state, 1 is built up by [Zn(C3H4N2)]2+ cations and NO3− anions interlinked by NH⋯O hydrogen bonds which give rise to the formation of a 3D network. Complex 1 and [CdNa2(µ-L2)]n·6.34H2O (2), (L = 2-(2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl)terephthalate) were used as catalysts for the Henry reaction, and high yields were obtained under optimum conditions. Both 1 and 2 act as very efficient catalysts for the Henry reaction and convert nitroethane and aldehydes to β-nitroalcohols in yields of up to 89%. The threo/erythro diastereoselectivity depends on the choice of catalyst and also the selection of the reaction substrate, reaching values up to 89:11.