Vinyl Glycosides in Oligosaccharide Synthesis. 2. The Use of Allyl and Vinyl Glycosides in Oligosaccharide Synthesis.

A novel latent-active glycosylation strategy has been described that relies on the isomerization of substituted allyl glycosides to give the corresponding vinyl glycosides, which can subsequently be used in Lewis acid-mediated glycosylations. The isomerization reaction was performed by a rhodium catalyst obtained by treating tris(triphenylphosphine)rhodium(I) chloride with n-butyllithium. This catalyst has many advantageous properties over the use of conventional Wilkinson's catalyst. The glycosylation reactions gave high yields for both primary and secondary sugar alcohols, and the anomeric selectivity could be controlled by the constitution of the glycosyl donor and reaction conditions. The new isomerization and glycosylation approach enables complex oligosaccharides of biological importance to be prepared in a highly convergent manner.