The Use of Grignard Reagents in the Synthesis of Carbohydrates. III. The One-way Anomerization of Methyl Glycofuranosides and the Opening of Their Furanose Rings

Abstract

Abstract The anomerization of methyl glycofuranoside derivatives with methylmagnesium iodide or t-butylmagnesium bromide occurred in a one-way manner. For example, methyl 5-O-benzyl-β-d-ribofuranoside (3β) was converted into the corresponding α-anomer (3α) in a 95% yield when a mixture of 3β and t-butylmagnesium bromide in benzene–ether was heated at about 75 °C to remove the ether; the reverse reaction (from 3α to (3β) did not proceed. The reaction of 3β with methylmagnesium iodide gave open-chain products (33%), besides 3α (30%). Twenty kinds of anomers were tested, and the mechanisms of the reactions were discussed. The cleavage of a benzyl- or trityl-protecting group with the Grignard reagent was also observed during the reaction.