Halogen addition to some 1-C-substituted pyranoid glycals.

Addition of bromine and chlorine to O-peracylated 1-CN-, COOMe- and CONH-substituted glycals was studied under ionic and radical conditions. The main or exclusive products were the corresponding 2,3-trans-diaxial (3-bromo-3-deoxy-α-d-heptopyranosylbromide)onic acid derivatives. Bromination of the O-peracetylated d-lyxo-hept-2-enopyranosononitrile and all chlorinations proved selective towards the 2-axial-3-equatorial (3-halogeno-3-deoxy-α-d-heptopyranosylhalide)onic acid derivatives. Silver triflate promoted glycosylation of methanol was successful with each 2,3-trans-diaxial (3-bromo-3-deoxy-α-d-heptopyranosylbromide)onic acid derivative, however, several attempted nucleophilic substitution and elimination reactions gave the parent glycal only.