The intermolecular migration of polyol stannylenes as a reaction contributing to the regioselectivity of substitution

Abstract Pairs of the partially protected glycosides benzyl 4,6- O -benzylidene-β- d -galactopyranoside, benzyl 2,3-di- O -benzyl-β- d -galactopyranoside, benzyl 2,6-di- O -benzyl-α- d -galactopyranoside, and benzyl 2,3-di- O -benzyl-α- d -glucopyranoside were treated with equimolar proportions of Bu 2 SnO in benzene in the conditions of stannylene formation, and the resulting mixture was benzoylated in situ with benzoyl chloride. Estimation of the product of benzoylation led to the following order of reactivity in the stannylenation reaction: 2,3-diol>4,6-diol, and 2,3-diol>3,4-diol. An intermolecular migration of dibutyltin between sugars was demonstrated. It is considered that these migrations contribute efficiently to the regiospecificity of the stannylene reaction.