New pathways toward the synthesis of polyketide-like macrolides have been developed through the functionalization of long chain polyolic fragments readily obtained from 3,3'-methylenebis{[6-(benzyloxy)methoxy]cyclohept-3-en-1-ol} derivatives 6. This synthetic route generates a large variety of stereoisomers and thus can be applied to the preparation of a library of polyhydroxylated macrocycles, analogues of natural bioactive macrolides.