Graduate Thesis Or Dissertation
 

Synthetic studies toward the total synthesis of amphidinolide B₁

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  • Amphidinolide B₁ is one of the most potent cytotoxic compounds in the amphidinolide family. Its bioactivity and intriguing structure has drawn attention from synthetic chemists. Although numerous synthetic efforts toward the total synthesis of amphidinolide B₁ have been published, it still remains an unconquered synthetic target. One of the unique structural features of amphidinolide B₁ is the C₁₃-C₁₅ highly substituted diene. While most other synthetic groups tried to apply palladium or copper-mediated cross coupling methodologies to form this functionality, we elaborated this subtle moiety with a novel TiCl₄-mediated Fleming-type coupling and subsequent dehydration sequence. Our convergent strategy featured a highly diastereoselective aldol condensation of western aldehyde 104 and eastern ketone 105. This result is in stark contrast to prior efforts using similar approaches. The macrocyclic ring was established via a spontaneous intramolecular Wadsworth-Emmons olefination with excellent yield and stereoselectivity. A novel approach toward the formation of the unusual ally! epoxide moiety was affectedwith an oxidative elimination of the selenide species 416 to give the allyl epoxide 417 as a single isomer. The only challenge remaining in this total synthesis is two deprotection steps. After extensive experimentation, we discovered that the PMB protection group had to be removed before the macrolactonization and the incorporation of the allyl epoxide functionality. After deprotection of the PMB ether, a global desilylation will complete the total synthesis of amphidinolide B₁.
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