| Summary: | <p>This thesis describes the synthesis and intramolecular cycloaddition products of azides tethered to olefins bearing a heteroatom in an attempt to access a proposed triazolium intermediate 77.</p> <p>Chapter 1 covers the synthesis and reactivity of simple di- and trisubstituted azidoalkyl enol ethers. These substrates were found to provide isolable 1,2,3-triazoline products, but displayed a propensity to aromatise to 1,2,3-triazoles upon ionisation. Difficulties in synthesising fully-substituted azidoalkyl enol ethers have precluded a detailed study in this project, though a bias towards α-alkoxy imine formation was suggested.</p> <p>Chapter 2 covers the chemistry of azidoalkyl vinyl bromides. Simple vinyl bromide substrates were found to yield 1-azadienes upon thermolysis, presumably <em>via</em> the dehydrobromination of an α-bromo imine intermediate <em>in situ</em>.</p> <p>In Chapter 3, a brief diversity-oriented synthesis (DOS) campaign was undertaken to demonstrate the potent reactivity of 1-azadiene substrates. 1-Azadienes were found to be versatile intermediates, and a small DOS library was built by exploiting several key reactivity modes.</p> <p>In Chapter 4, two miscellaneous routes towards the desired triazolium intermediate are discussed, and finally an Appendix chapter deals with an attempted total synthesis of salinosporamide C.</p>
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