Graduate Thesis Or Dissertation
 

Approaches to the total synthesis of verrucarol

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  • Verrucarol is the sesquiterpene portion of a number of macrocyclic di- and triesters of potential medicinal importance. In this study, a novel approach to the synthesis of this fungal metabolite is presented. An A-B-C route was investigated in which C-3 and C-4 of the C-ring were emplaced using a [2+2] photocycloaddition reaction between acetylene or ketene dimethyl acetal and an A-B ring synthon such as cis-3-Acetoxy-4a-carbomethoxy-4-methy1-7,7- ethylenedioxy-4a,5,6,7,8,8a-hexahydrocoumarin (121). The photoaddition reactions were not successful in cases where the A-B ring synthon was substituted at the 3- position but otherwise proceeded in approximately 70% yield to give single stereoisomers of the desired cyclobutenes or cyclobutanes. Ring expansion of these photoadducts to afford the trichothecene skeleton was attempted using several methodologies. In one attempt, cis-anti-cis-6,6,- Dimethoxy- 7-methy1-8-carbomethoxy-11,11-ethylenedioxy-2-oxatricyclo[6.4.0.0⁴'⁷]dodec-3-one (133) was subjected to potassium pyrosulfate in refluxing xylene in a variation of the Cargill reaction. This reaction proceeded by an alternative mechanism to yield bicyclobutane 137. Other attempted ring expansions on similar lactones or lactol derivatives also failed to afford the desired ring skeleton.
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