Synthesis of naphthyl C-glycosides of rearranged tri-O-benzyl-2-deoxy-d-glucose

C-Glycosylation of 3-bromonaphthol 4 with benzyl-protected glycosyl donor 19 afforded rearranged bicyclic acetal 24 in which the glycosyl donor had undergone an unusual 1,6-hydride shift. Use of the regioisomeric 2-bromonaphthol 6 with the same glycosyl donor 19 afforded the expected β-C-glycoside 22.