Synthetic endeavours in nitrogen heterocycles: palladium mediated domino reactions, novel rearrangements and efforts towards a total synthesis of arboflorine

Charles Heath

Research output: ThesisDoctoral Thesis

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Abstract

This thesis describes our synthetic endeavours in nitrogen containing heterocyclic compounds. The work included several key themes including the pursuit of biologically active compounds, the development of elegant and environmentally benign procedures including domino reactions. The use of palladium mediated transformations in organic synthesis, the construction of new unknown ring systems and the structural elucidation of heterocyclic compounds including the structural elucidation of natural products by synthesis have also been explored. Chapter 2 describes our synthetic investigations of the 3-benzazepines I and azepino[4,5-b]indoles II. Through the use of the palladium catalysed Tsuji-Trost reaction followed by a Heck reaction we were able to devise a synthetic approach to access these N-heterocycles. We were able to synthesize simple derivatives of both I and II in addition to more complex compounds featuring additional fused rings by including the use of different cyclic and acyclic allylic substrates for the Tsuji-Trost reaction. After the development of the single step Tsuji-Trost/Heck synthetic protocols for these compounds we successfully combined these two reactions into a single pot domino reaction. In addition to Tsuji-Trost/Heck domino reactions we have also developed a Heck/carbopalladation domino reaction for the synthesis of an azepino[3,4,5-hi]benz[b]indolizine derivative. Chapter 3 describes our attempts to synthesize the natural product arboflorine. We initially began with attempts to elaborate the azepino[4,5-b]indoles synthesized in Chapter 2 to provide arboflorine, however this did not prove fruitful. In the course of this investigation we discovered a novel rearrangement of an azepino[4,5-b]indole to give the peroxide IV which became the topic of Chapter 4.
Original languageEnglish
QualificationDoctor of Philosophy
Publication statusUnpublished - 2011

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