RESUMEN
The title cluster (Pd(3)(2+)) exhibits a pronounced affinity for Br(-) ions to form the very stable Pd(3)(Br)(+) adduct. Upon a 2-electron reduction, a dissociative process occurs generating Pd(3)(0) and eliminating Br(-) according to an ECE mechanism (electrochemical, chemical, electrochemical). At a lower temperature (i.e. -20 degrees C), both ECE and EEC processes operate. This cluster also activates the C-Br bond, and this work deals with the reactivity of Pd(3)(2+) with 2,3,4-tri-O-acetyl-5-thioxylopyranosyl bromide (Xyl-Br), both alpha- and beta-isomers. The observed inorganic product is Pd(3)(Br)(+) again, and it is formed according to an associative mechanism involving Pd(3)(2+).Xyl-Br host-guest assemblies. In an attempt to render the C-Br bond activation catalytic, these species are investigated under reduction conditions at two potentials (-0.9 and -1.25 V vs SCE). In the former case, the major product is Xyl-H, issued from a radical intermediate Xyl(*) abstracting an H atom from the solvent. Evidence for Xyl(*) is provided by the trapping with TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) and DMPO (5,5'-dimethylpyrroline-N-oxyde). In the second case, only one product is observed, 3,4-di-O-acetyl-5-thioxylal, which is issued from the Xyl(-)() intermediate anion.
RESUMEN
Electroreduction of the disulfide derivative RSSR (5, R= [bond]C(6)H(4)[bond]CO[bond]C(6)H(4)[bond]CN) on a mercury pool or a carbon gauze electrode in the presence of 2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl bromide (1), using a sacrificial zinc anode gave an alpha,beta anomeric mixture of [4-(4-cyanobenzoylphenyl)] 2,3,4-tri-O-acetyl-1,5-dithio-D-xylopyranoside (6) in 40-70% yield, according to the experimental conditions used (nature of solvent, electrolyte salt, and temperature). High selectivity favouring the alpha anomer of 6 is observed starting from the alpha anomer of 1. Mechanistic aspects are discussed.
