Bioinspired Total Synthesis of Natural Products

Abstract

This work describes the divergent total syntheses of ten structurally complex pallavicinia diterpenoids with three distinct carbon skeletons through chemical emulation of the biogenic skeletal diversification process. of lactone 12 with PIFA and BF 3 •Et 2 O to form the C10a−C10b bond by bioinspired oxidative coupling followed by DDQmediated oxidation afforded the desired 13. Finally, compound 13 was readily converted to lamellarins D/H (14/7) via deprotection, respectively.In this work, we have achieved the total synthesis of lamellarins D/H (14/7) in seven steps and ningalin B (6) in five steps in a bioinspired manner. Especially, the synthesis of lamellarins D/H (14/7) features three bioinspired oxidative coupling reactions to generate three rings by the formation of key C−C and C−O bonds.Encouraged by the described syntheses, we expected further employment of this bioinspired approach in the construction of more complex natural products. Scheme 2. Proposed Biosynthesis of Clavicipitic Acid and Pd-Catalyzed Olefination Scheme 3. Bioinspired Total Synthesis of Clavicipitic Acid Accounts of Chemical Research pubs.acs.org/accounts Article