Shigenobu Yano

Reactions of metal complexes with carbohydrates: Synthesis and characterization of novel nickel(II) complexes containing glycosylamines derived from a monosaccharide and a diamine. An X-ray crystallographic study of (ethylenediamine) {N-(2-aminoethyl)-d-fructopyranosylamine} nickel(II) · Cl2 · CH3OH

Abstract Tris(ethylenediamine)- or tris(trimethylenediamine)-nickel(II) salts react with d -glucose, d -mannose, or d -fructose to give novel, octahedral, nickel(II) complexes containing glycosylamine(s) derived from the reaction of the monosaccharide with the diamine. The complexes have been characterized by elemental analysis, magnetic susceptibility, and electronic absorption, infrared, and circular dichroism spectra. The complexes from aldoses contain two sugar entities, and those from a ketose have one sugar unit. The X-ray crystal structure was determined of one of the products, in which N -(2-aminoethyl)- d -fructopyranosylamine and ethylenediamine are coordinated to a nickel ion. Crystal data for the compound: a = 12.348(5) A, b = 18.478(8) A, c = 8.464(4) A, Z = 4, space group P2 1 2 1 2 1 , 2348 unique observed reflections [Fo > 3σ(Fo)] used in the structure analysis, R = 0.068, Rw = 0.053. The sugar is coordinated to the nickel ion at three points, through the 1- and 3-hydroxyl groups and the nitrogen atom on C-2.

Evidence for the C-N Bond Formation Between An Aldose and Ethylenediamine on Cobalt(III) Complexes. Deuterium Isotope Effects on Carbon-13 NMR Chemical Shifts

Abstract We have already reported the synthesis and characterization of Co(III) complexes containing an N-glycoside derived from ethylenediamine (en) and an aldose. 1 In the report, the formation of a new C-N bond has been presumed according to the chemical shifts of the 13C signals originated from the en units in their 13C NMR spectra: one of the signals assigned to the en carbon atoms, which is presumably corresponding to the carbon atom adjacent to the glycosidic nitrogen, appears at 7–8 ppm downfield from the other three.