Diastereoselective Total Synthesis of (+/-)-Basiliolide B and (+/-)-epi-8-Basiliolide B

The C8 and C9 stereogenic centers of the basiliolide/transtaganolide family have been established stereoselectively using a cyclopropane ring-opening strategy, which has been studied by DFT calculations of a variety of lithium,Chelating models. The highly functionalized intermediates obtained in this strategy were successfully employed for the diastereoselective total synthesis of (+/-),basiliolide B and (+/-)-epi-8-basiliolide B. The decalin core with a lactone bridge was constructed via a 2-pyrone Diels-Alder (DA) cycloaddition, and the unprecedented seven-membered acyl ketene acetal was established by a biorhimetie intramolecular O-acylation cyclizdtion.