Defaut, benedicte (2011)
Ph.D. thesis, University of Birmingham.
Dictyoxetane, a structurally novel diterpene, is related to the dollabellane class of natural products. Dictyoxetane contains a dioxatricyclic subunit that has never been encountered in any other natural product. This thesis describes studies towards a first total synthesis of dictyoxetane, based on a proposed intramolecular Paternò-Büchi [2+2] photocyclisation reaction between a ketone and a cyclic enol ether to generate the oxetane heterocycle of the natural product. Chapter 1 introduces the dolabellanes. The isolation, structure and proposed biosynthesis of dictyoxetane are discussed, along with existing synthetic studies towards the core dioxatricyclic ring system. Key aspects of the Paternò-Büchi reaction of alkenes with carbonyl compounds are presented. In Chapter 2 a model system, designed to test the key Paternò-Büchi [2+2] photocyclisation reaction, is proposed. A number of strategies are investigated for the overall conversion of the double bond of isopulegol into a six-membered ring enol ether. Chapter 3 describes studies towards the synthesis of the [4.3.0]-trans-hydrindane ring system contained within dictyoxetane, a structural feature that has yet to be addressed in the literature. Chapter 4 contains the experimental procedures and analytical data of all compounds prepared during the course of this study.
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