Two-step synthesis of per-O-acetylfuranoses: optimization and rationalization

Abstract

A simple two-step procedure yielding peracetylated furanoses directly from free aldoses was implemented. Key steps of the method are (i) highly selective formation of per-O-(tert-butyldimethylsilyl)furanoses and (ii) their clean conversion into acetyl ones without isomerization. This approach was easily applied to galactose and structurally related carbohydrates such as arabinose, fucose, methyl galacturonate and N-acetylgalactosamine to give the corresponding peracetylated targets. The success of this procedure relied on the control of at least three parameters: (i) the tautomeric equilibrium of the starting unprotected oses, (ii) the steric hindrance of both targeted furanoses and silylating agent, and finally, (iii) the reactivity of each soft nucleophile during the protecting group interconversion.