Catalyst and substrate effects in enantioselective C–H insertion reactions of α-diazosulfones

This thesis describes a systematic investigation of the mechanistic and synthetic aspects of intramolecular reactions of a series of α-diazo-β-oxo sulfone derivatives using copper and, to a lesser extent, rhodium catalysts. The key reaction pathways explored were C–H insertion and cyclopropanation, with hydride transfer competing in certain instances. Significantly, up to 98% ee has been achieved in the C–H insertion processes using copper-NaBARF-bisoxazoline catalysts, with the presence of the additive NaBARF critical to the efficiency of the transformations. This novel synthetic methodology provides access to a diverse range of enantioenriched heterocyclic compounds including thiopyrans, sulfolanes, β- and γ-lactams, in addition to carbocycles such as fused cyclopropanes. The synthesis of the α-diazosulfones required for subsequent investigations is initially described. Of the twenty seven diazo sulfones described, nineteen are novel and are fully characterised in this work. The discussion is subsequently focused on a study of the copper and rhodium catalysed reactions of the α-diazosulfones with Chapter Four concentrated on highly enantioselective C–H insertion to form thiopyrans and sufolanes, Chapter Five focused on C–H insertion to form fused sulfolanes, Chapter Six focused on C–H insertion in sulfonyl α-diazoamides where both lactam formation and / or thiopyran / sulfolane formation can result from competing C–H insertion pathways, while Chapter Seven focuses on cyclopropanation to yield fused cyclopropane derviatives. One of the key outcomes of this work is an insight into the steric and / or electronic factors on both the substrate and the catalyst which control regio-, diastereo- and enantioselectivity patterns in these synthetically powerful transformations. Full experimental details for the synthesis and spectral characterisation of the compounds are included at the end of each Chapter, with details of chiral stationary phase HPLC analysis and assignment of absolute stereochemistry included in the appendix.

Saint, martyr, killer of Christ? The legend of Longinus in medieval Irish tradition

This dissertation is the first comprehensive and synthetic study of the Irish presentation and legends of Longinus. Longinus was the soldier at the crucifixion who pierced Christ with a spear, who believed and, according to some texts, was healed of his blindness by the blood and water issuing from the wound, and who later was martyred for his belief. In my thesis I survey the knowledge and use of the legend of Longinus in Ireland over genres and over time. Sources used for the analyses include iconographic representations of the spear-bearer in manuscripts, metalwork and stone and textual representations of the figure of Longinus ranging over the history of Irish literature from the early medieval to the early modern period, as well as over Irish and HibernoLatin texts. The thesis consists of four core chapters, the analyses of the presentations of Longinus in early-medieval Irish texts and in the iconographic tradition (I,II), the editions of the extant Irish and the earliest surviving Latin texts of the Passion of Longinus and of a little-known short tract describing the healing of Longinus from Leabhar Breac (III), and the discussion of the later medieval Irish popular traditions (IV). Particular attention is given to the study of two intriguing peculiarities of the Irish tradition. Most early Irish Gospel books feature an interpolation of the episode of the spear-thrust in Matthew 27:49, directly preceding the death of Christ, implying its reading as the immediate cause of death. The image of Longinus as 'iugulator Christi' ('killer of Christ') appears to have been crucial for the development of the legend. Also, the blindness motif, which rarely features in other European popular traditions until the twelfth century, is attested as early as the eighth century in Ireland, which has led some scholars to suggest a potential Irish origin.