Enantioselective and Collective Total Syntheses of Xanthanolides

Abstract

AbstractAn enantioselective synthesis of (+)‐8‐epi‐xanthatin hinging on a chiral phosphoric acid catalyzed tandem allylboration/lactonization reaction is reported. With (+)‐8‐epi‐xanthatin as the precursor, the collective synthesis of a series of synthetically challenging xanthanolides was also accomplished. Among them, xanthipungolide, one of the most complex xanthanolide monomers, was accessed through a bioinspired tandem double‐bond isomerization/6π electronic cyclization/intramolecular Diels–Alder reaction, and pungiolides A, B, D, E, and L–N, a group of xanthanolide dimers, were assembled through a bioinspired Diels–Alder dimerization followed by late‐stage diversification.