Towards the total synthesis of amphidinolides C and F

The amphidinolides are marine macrolides extracted from dinoflagellates of the genus Amphidinium. To date, 37 amphidinolides have been isolated and identified, most of them possessing cytotoxicity against human cancer cell lines. Among these, amphidinolides C, F, C2 and C3 represent synthetic targets of interest owing to their scarcity, structural complexity and promising biological activities. This thesis describes the work realised towards the total synthesis of amphidinolides C and F, with a focus on the different strategies investigated and the key fragments synthesised. In the first approach, the C18−C29 fragment of amphidinolide F was prepared using an intramolecular etherification of an epoxide under acidic catalysis to produce the 2,5-trans-disubstituted tetrahydrofuran ring featured in the natural product. Unfortunately, dithiane alkylation with the C1−C17 iodide counterpart generated the desired coupling product in low yield. A second approach proposing to build the C17−C18 bond by a silicon-tethered RCM proved unsuccessful, because the requisite diene could not be obtained. It was then envisioned to form the C18−C19 bond by displacement of a triflate with an alkyne and install the ketone at C18 by a protoborylation/oxidation sequence. To this end, the C19−C29 triflate precursor was synthesised. Displeasingly, the C1−C18 alkyne counterpart (work by Dr Filippo Romiti) could not be prepared and coupling of the two fragments was not attempted. In the latest approach, the C10−C29 fragment of amphidinolide F was obtained employing a boron-mediated aldol condensation and a dithiane alkylation to form the C13−C14 and C18−C19 bonds. Several endgame strategies were examined including the successful Yamaguchi esterification of the C13-epi C10−C29 fragment and the C1−C9 acid. A challenging Stille crosscoupling was then effected to close the macrocycle but only yielded the desired macrolactone in trace amounts after global desilylation.

Warfare in the West Highlands and Isles of Scotland, c. 1544-1615

Warfare has long been associated with Scottish Highlanders and Islanders, especially in the period known in Gaelic tradition as ‘Linn nan Creach’ (the ‘Age of Forays’), which followed the forfeiture of the Lordship of the Isles in 1493. The sixteenth century in general is remembered as a particularly tumultuous time within the West Highlands and Isles, characterised by armed conflict on a seemingly unprecedented scale. Relatively little research has been conducted into the nature of warfare however, a gap filled by this thesis through its focus on a series of interconnected themes and in-depth case studies spanning the period c. 1544-1615. It challenges the idea that the sixteenth century and early seventeenth century was a time of endless bloodshed, and explores the rationale behind the distinctive mode of warfare practised in the West Highlands and Isles. The first part of the thesis traces the overall ‘Process of War’. Chapter 1 focuses on the mentality of the social elite in the West Highlands and Isles and demonstrates that warfare was not their raison d'être, but was tied inextricably to chiefs’ prime responsibility of protecting their lands and tenants. Chapter 2 assesses the causation of warfare and reveals that a recurrent catalyst for armed conflict was the assertion of rights to land and inheritance. There were other important causes however, including clan expectation, honour culture, punitive government policies, and the use of proxy warfare by prominent magnates. Chapter 3 takes a fresh approach to the military capacity of the region through analysis of armies and soldiers, and the final thematic chapter tackles the conduct of warfare in the West Highlands and Isles, with analysis of the tactics and strategy of militarised personnel. The second part of this thesis comprises five case studies: the Clanranald, 1544-77; the Colquhouns of Luss and the Lennox, 1592-1603; the MacLeods of Harris and MacDonalds of Sleat, 1594-1601; the Camerons, 1569-1614; and the ‘Islay Rising’, 1614-15. This thesis adopts a unique approach by contextualising the political background of warfare in order to instil a deeper understanding of why early modern Gaelic Scots resorted to bloodshed. Overall, this period was defined by a sharp rise in military activity, followed by an even sharper decline, a trajectory that will be evidenced vividly in the final case study on the ‘Islay Rising’. Although warfare was widespread, it was not unrestrained or continuous, and the traditional image of a region riven by perpetual bloodshed has been greatly exaggerated.

Eighty years 'Owre the Sea': Robert Burns and the early United States of America, c. 1786-1866.

This thesis represents the first extensive critical study of the relationship between Robert Burns and the early United States of America. Spanning literature, history and memory studies, the following chapters take an interdisciplinary approach towards investigating the methods by which Burns and his works rose to prominence and came to be of cultural and literary significance in America. Theoretically, these converging disciplines intersect through a transnational, Atlantic Studies perspective that shifts emphasis from Burns as the 'national poet of Scotland' onto the various socio-cultural connections that facilitated the spread of his work and reputation. In addition to Scottish literary studies, the thesis contributes to the broader fields of Transatlantic, Transnational and American Studies. Previous studies have suggested that Burns's popularity in the early United States might be attributed to his kinship with 'national' American ideals of freedom, egalitarianism and individual liberty. While some of the evidence supports this claim, this thesis argues that it also wrongly assumes a spatiotemporal unity for the nineteenth-century American nation. It concludes by suggesting that future critical studies of the poet must heed the multifarious complexities of 'national' paradigms, pointing the way to further work on the reception and influence of Burns in other 'global' or, indeed, transnational contexts.

Graphic satire and the rise and fall of the First British Empire: political prints from the Seven Years' War to the Treaty of Paris, c. 1756-1783

This thesis examines the early stages of the transformation of emblematic political prints into political caricature from the beginning of the Seven Years' War (1756) to the Treaty of Paris, which ended the American Revolutionary War (1783). Both contextual and iconographical issues are investigated in relation to the debates occasioned by Britain's imperial project, which marked a period of dramatic expansion during the Seven Years' War, and ended with the loss of the American colonies, consequently framing this thesis as a study of political prints during the rise and fall of the so-called 'First British Empire'. Previous studies of eighteenth-century political prints have largely ignored the complex and lengthy evolutionary process by which the emblematic mode amalgamated with caricatural representation, and have consequently concluded that political prints excluded emblems entirely by the end of the 1770s. However, this study emphasizes the significance of the Wilkite movement for the promotion and preservation of emblems, and investigates how pictorial political argument was perceived and received in eighteenth-century British society, arguing that wider tastes and opinions regarding the utilization of political prints gradually shifted to accept both modes of representation. Moreover, the marketplace, legal status, topicality, and manufacturing methods of political prints are analyzed in terms of understanding the precarious nature of their consumption and those that endeavoured to engage in political printmaking. The evolution, establishment, and subsequent appropriation of pictorial tropes is discussed from the early modern period to the beginning of the so-called Golden Age of caricature, while tracing the adaptation of representational models in American colonial prints that employed emblems already entrenched in British pictorial political debate. Political prints from the two largest print collections, the British Museum and the Lewis Walpole Library at Yale are consulted, along with a number of eighteenth-century newspapers and periodicals, to develop the earlier research by M. Dorothy George, Charles Press, Herbert Atherton, Diana Donald, Amelia Rauser, and Eirwen Nicholson.