The reaction of partially protected aldoses with stabilized arsonium ylides: Synthesis of E acyclic unsaturated derivatives and C-glycosyl derivatives

Article abstract of DOI:10.1016/S0008-6215(97)00148-1

The reaction of partially protected aldoses with (carbomethoxymethyl)triphenylarsonium bromide and zinc in toluene gave E α,β-unsaturated acyclic esters. When intramolecular transesterification occurred, bicyclic 1,4-lactone derivatives were formed concurrently. Otherwise, using these non alcaline conditions, olefination did not favour the formation of C-glycosyl derivatives. On the other hand, when the reaction was performed with (carbomethoxymethylene)triphenylarsorane in toluene, followed by the addition of n-butyllithium, bicyclic derivatives were obtained rapidly in good yields. Moreover, when cyanomethyltriphenylarsonium bromide was used in place of (carbomethoxymethyl)triphenylarsonium bromide, the corresponding E aldooctenonitriles were produced in satisfactory yields.