Radical Rearrangement of 2-O-(Diphenylphosphoryl)glycosyl Bromides. A New Synthesis for 2-Deoxy Disaccharides and 2-Deoxy Ribonucleosides

Article abstract of DOI:10.1021/jo00057a020

2-Deoxy-1-O-diphenylphosphoryl glycosides react with nucleophiles under mild conditions giving access to 2-deoxy disaccharides and nucleosides.The intermediate 2-deoxy-1-O-diphenylphosphoryl compounds were generated in situ by a radical 2 -> 1 migration of the phosphate ester group.This is the first observation of a rearrangement of a phosphate ester in radicals.ESR experiments and quenching of the radical at C2 by tin hydride or tin deuteride were used to detect the intermediates and to prove their structure.