A Biomimetic Synthesis of (±)‐Basiliolide B |
| |
| Authors: | Long Min Yang Zhang Xuefeng Liang Junrong Huang Wenli Bao Dr Chi‐Sing Lee |
| |
| Affiliation: | Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen University Town, Xili, Shenzhen 518055 (China) |
| |
| Abstract: | A highly diastereoselective and practical biomimetic total synthesis of (±)‐basiliolide B has been achieved through the study of the two proposed biosynthetic pathways (O‐methylation and O‐acylation) for the unprecedented 7‐methoxy‐4,5‐dihydro‐3H‐oxepin‐2‐one (C ring). The synthesis featured a cyclopropanation/ring opening strategy for establishing the stereogenic centers at C8 and C9, a biomimetic 2‐pyrone Diels–Alder cycloaddition for the synthesis of the ABD ring system, and finally a highly efficient biomimetic intramolecular O‐acylation for the C ring formation. This result provides an important perspective on the biosynthetic origin of the unprecedented 7‐membered acyl ketene acetal moiety of the C ring. |
| |
| Keywords: | Diels– Alder reaction basiliolide B biomimetic synthesis cyclopropanation O‐acylation |
|
|
