Covert conversations: disciplined improvisation and meaning-making in the masters (MA) supervisory relationship

This research asks the question: “What are the relational dynamics in Masters (MA) supervision?” It does so by focusing upon the supervisory relationship itself. It does this through dialoguing with the voices of both MA supervisors and supervisees in the Humanities using a Cultural Historical Activity Theory (CHAT) framework. In so doing, this research argues for a re-evaluation of how MA supervision is conceptualised and proposes a new theoretical framework for conceptualising MA supervision as a relational phenomenon. The research design was derived from an Activity Theory-influenced methodology. Data collection procedures included the administration of Activity Theory Logs, individual semi-structured interviews with both supervisors and supervisees and the completion of reflective journals. Grounded Theory was used to analyse the data. The sample for the study consists of three supervisor-supervisee dyads from three disciplines in the Humanities. Data was collected over the course of one academic year, 2010-2011. This research found that both individual and shared relational dynamics play an important role in MA supervision. Individual dynamics, such as supervisors’ iterative negotiation of ambiguity/clarity and supervisees’ boundary work, revealed that both parties attempt to negotiate a separation between their professional-academic identities and personal identities. However, an inherent paradox emerged when the shared relational dynamics of MA supervision were investigated. It was found that the shared space created by the supervisory relationship did not only exist in a physical setting, but was also psychoactive in nature and held strong emotional resonances for both parties involved. This served to undermine the separation between professional-academic and personal identities. As a result, this research argues that the interaction between the individual and shared relational dynamics in MA supervision enables, for both supervisors and supervisees, a disciplined improvisation of academic identity.

Copper-catalysed asymmetric sulfide oxidation

The focus of this thesis is the preparation of enantiopure sulfoxides by means of copper-catalysed asymmetric sulfoxidation, with particular emphasis on the synthesis of aryl benzyl and aryl alkyl sulfoxides. Chapter 1 contains a review of the methods employed for the asymmetric synthesis of sulfoxides, compounds with many applications in stereoselective synthesis and in some cases with pharmaceutical application. Chapter 1 describes asymmetric oxidation, including metal-catalysed, non metal-catalysed and enzyme-catalysed, in addition to synthetic approaches via nucleophilic substitution of appropriately substituted precursors. Kinetic resolution in oxidation of sulfoxides to the analogous sulfones is also discussed; in certain cases, access to enantioenriched sulfoxides can be achieved via a combination of asymmetric sulfoxidation and complementary kinetic resolution. The design and synthesis of a series of sulfides to enable exploration of the substituent effects of the copper-mediated oxidation was undertaken, and oxidation to the racemic sulfoxides and sulfones to provide reference samples was conducted. Oxidation of the sulfides using copper-Schiff base catalysis was undertaken leading to enantioenriched sulfoxides. The procedure employed is clean, inexpensive, not air-sensitive and utilises aqueous hydrogen peroxide as oxidant. Extensive investigation of the influence of the reaction conditions such as solvent, temperature, copper salt and ligand was undertaken to lead to the optimised conditions. While the direct attachment of one aryl substituent to the sulfide is essential for efficient enantiocontrol, in the case of the second substituent the enantiocontol is dependent on the steric rather than electronic features of the substituent. Significantly, use of naphthyl-substituted sulfides results in excellent enantiocontrol; notably 97% ee, obtained in the oxidation of 2-naphthyl benzyl sulfide, represents the highest enantioselectivity reported to date for a copper-mediated sulfur oxidation. Some insight into the mechanistic features of the copper-mediated sulfur oxidation has been developed based on this work, although further investigation is required to establish the precise nature of the catalytic species responsible for asymmetric sulfur oxidation. Full experimental details, describing the synthesis and structural characterisation, and determination of enantiopurity are included in chapter 3.