Organocatalytic enantioselective synthesis of 1,3,5-polyols by means of iterative asymmetric epoxidation: their application to the total synthesis of polyrhacitide A

We have developed a pragmatic route to the stereogenic skipped 1,3,5-polyols. The strategic transformation includes an organocatalytic enantioselective asymmetric epoxidation, which is either syn- or anti-selective as genesis of chirality and successive SN2 opening reaction by an appropriate functionalized nucleophile, followed by hydroboration/oxidation to generate stereoisomers in good yield. The critical intermediate generated en route to this process is employed in the total synthesis of polyrhacitide A.