Nucleophilic opening of bis-epoxide 1 derived from d-mannitol by organolithium species in the presence of boron trifluoride etherate allows the synthesis of enantiopure polyhydroxy tetrahydrofurane skeletons with aromatic moieties in the pseudo-anomeric position. ortho-Lithiation and transmetalation are the most appropriate conditions for the preparation of the organometallic derivatives where halogen–metal exchange is unfavorable.