Total Synthesis of (+)-3-Deoxyfortalpinoid†F, (+)-Fortalpinoid†A, and (+)-Cephinoid†H.

3-Deoxyfortalpinoid F, fortalpinoid A, and cephinoid H are members of the Cephalotaxus diterpenoids class of natural products, which feature diverse chemical structures and valuable biological activities. We report herein the development of a diastereoselective Pauson-Khand reaction as an effective pathway to access the core tetracyclic skeleton, which is found widely in Cephalotaxus diterpenoids. Furthermore, we enabled the construction of the tropone moiety through a ring-closing metathesis/elimination protocol. Based on the developed strategy, asymmetric synthesis of the title compounds has been achieved for the first time.

Total Synthesis of (-)-Ceforalide B and (-)-Cephanolides B-D.

(-)-Ceforalide B (1) and (-)-cephanolides B-D (2-4) are benzenoid cephanolide diterpenoids possessing the same pentacyclic skeleton, which contains three C13-C15 substituent patterns and different benzylic oxidation states. An olefination/6π-electrocyclization/oxidative aromatization cascade has been verified as divergent access to three C13-C15 patterns. The benzylic aerobic oxidations enabled by the Co(OAc)2·4H2O/bromide salt/O2/PPh3/N-hydroxyphthalimide system have been developed to deliver expected site-selectivity and different oxidation states. Through the divergent strategy, total synthesis of (-)-ceforalide B and (-)-cephanolides B-D is accomplished.