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Title: Synthesis of mono- and bicyclic azacycles via palladium- and ruthenium-catalysed enynamide cycloisomerisation
Author: Walker, P. Ross
ISNI:       0000 0004 5369 4413
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2014
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The initial aim of this project was to investigate ways of synthesising fused, spirocyclic and linked bicyclic amines. We built on methodology previously developed within our group, employing cyclic dienamides, prepared using the reductive cyclisation of bromoenynamides, as key structural building blocks for further annulation. In the course of investigating the reactivity of these cyclic dienamides, we discovered a new efficient and general route to their synthesis, by employing palladium- or ruthenium-catalysed enynamide cycloisomerisation. A wide range of attractive dienamide scaffolds were synthesised from simple enynamide precursors in rapid, high yielding and operationally simple reactions, underlining their potential utility as an atom-economical source of azacycles. Chiral enynamide substrates were used to generate 1,4-dienamides as a single diastereomer at the newly formed (quaternary) stereocentre. This relay of stereochemistry was exploited not only in the formation of monocyclic dienamides, but even in the formation of a spirocyclic product, and this bodes well for further stereocontrolled synthesis of polysubstituted azacycles. Finally the palladium- and ruthenium-catalysed cycloisomerisation of enynamides was discussed and investigated mechanistically, utilising 1H NMR spectroscopy, timecourse and deuterium-labelling experiments.
Supervisor: Anderson, Edward A. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Chemistry & allied sciences ; Organic chemistry ; Organic synthesis ; Heterocyclic chemistry ; Catalysis ; NMR spectroscopy ; cyclisation ; heterocycles ; ynamide ; palladium ; cycloisomerisation ; homogeneous catalysis