Abstract Polyprenols, a universal class of glycan-carrier lipids, play important roles in glycan biosynthesis in wide variety of living organisms. The chemical synthesis of natural polyisoprenols such as undecaprenol and dolichols, and even more so the synthesis of their homologs, could serve as a powerful way to investigate and define the functions of enzymes involved in glycan biosynthesis. In this paper, we report an efficient and reliable method to ...