Doctor of Philosophy
School of Chemistry and Molecular Bioscience
The research undertaken in this thesis aimed at the synthesis of nitrogen containing heterocycles which are a class of molecules highly sought after by chemical industry and academia. Cycloisomerisation reactions of 𝜋-rich species containing a pendant nitrogen atom was hypothesised as an expedient route to these heterocycles. As well as providing high-value products, such systems provide an arena for furthering the fundamental understanding of cycloisomerisation reactivity. Their synthesis was attempted either by purely organic reactions or mediated by a transition metal catalyst.
Azirididines were tested with Ni(0) and Pd(0)–catalysts and allenyl metals reagents in ring opening reactions for the synthesis of 𝛽-amino allenes. Unfortunately, this reaction proved challenging and an alternative route to 𝛽-amino allenes was investigated which involved reduction of 1,3-enynes with LiAlH4 and Lewis acid catalysed ring opening of 2-phenyl aziridine with propargylic-TMS. The synthesised 𝛽-amino allenes were then investigated in cycloisomerisation reactions with Au(I) and Ag(I)–catalysts. The Au(I)–catalysts favoured the formation of pyrrolidines while Ag(I)–catalysts favoured the formation of tetrahydropyridines.
Joyce, Liam Michael, Towards the Synthesis of Nitrogen Containing Heterocycles, Doctor of Philosophy thesis, School of Chemistry and Molecular Bioscience, University of Wollongong, 2022. https://ro.uow.edu.au/theses1/1350
FoR codes (2020)
3405 Organic chemistry
Unless otherwise indicated, the views expressed in this thesis are those of the author and do not necessarily represent the views of the University of Wollongong.