New methods for the asymmetric synthesis of α-alkylated ketones and 1,3-amino alcohols

A large number of optically active drugs and natural products contain α-functionalised ketones or simple derivatives thereof. Furthermore, chiral α-alkylated ketones are useful synthons and have found widespread use in total synthesis. The asymmetric alkylation of ketones represents one of the most powerful and longstanding procedures in organic chemistry. Surprisingly, however, only one effective methodology is available, and this involves the use of chiral auxiliaries. This is discussed in Chapter 1, which also provides a background of other key topics discussed throughout the thesis. Expanding on the existing methodology of chiral auxiliaries, Chapter 2 details the synthesis of a novel chiral auxiliary containing a pyrrolidine ring and its use in the asymmetric preparation of α-alkylated ketones with good enantioselectivity. The synthesis of racemic α-alkylated ketones as reference standards for GC chromatography is also reported in this chapter. Chapter 3 details a new approach to chiral α-alkylated ketones using an intermolecular chirality transfer methodology. This approach employs the use of simple non-chiral dimethylhydrazones and their asymmetric alkylation using the chiral diamine ligands, (+)- and (-)-sparteine. The methodology described represents the first example of an asymmetric alkylation of non-chiral azaenolates. Enantiomeric ratios up to 83 : 17 are observed. Chapter 4 introduces the first aldol-Tishchenko reaction of an imine derivative for the preparation of 1,3-aminoalcohol precursors. 1,3-Aminoalcohols can be synthesised via indirect routes involving various permutations of stepwise construction with asymmetric induction. Our approach offers an alternative highly diastereomeric route to the synthesis of this important moiety utilising N-tert-butanesulfinyl imines in an aldol-Tishchenko-type reaction. Chapter 5 details the experimental procedures for all of the above work. Chapter 6 discusses the results of a separate research project undertaken during this PhD. 2-alkyl-quinolin-4-ones and their N-substituted derivatives have several important biological functions such as the role of Pseudomonas quinolone signal (PQS) in quorum sensing. Herein, we report the synthesis of its biological precursor, 2-heptyl-4-hydroxy-quinoline (HHQ) and possible isosteres of PQS; the C-3 Cl, Br and I analogues. N-Methylation of the iodide was also feasible and the usefulness of this compound showcased in Pd-catalysed cross-coupling reactions, thus allowing access to a diverse set of biologically important molecules.

The print block and the digital cylinder

Purpose – To consider the economic and physical impact of electronic journals on remotely stored print stock. Design/methodology/approach – A collection of print journals was used as an object for consideration. Physical and heritage aspects of the collection are examined and questions are posed regarding the wisdom of future retention in response to increased demand for electronic alternatives. Findings – Emerging trends predict a predominance of periodical literature in electronic form. The future of local remote storage for low demand printed journal collections needs to be evaluated in economic as well as cultural terms. Research limitations/implications – Based on a collection at the Boole Library, University College Cork, Ireland. Practical implications – Similar consideration should be given to collections in other regional libraries. Originality/value – Contributes to discussions on the long-term value of retaining print journal holdings.

Team-teaching for inclusive learning: Purposes, practices and perceptions of a team-teaching initiative in Irish post-primary schools

Background. Schools unequivocally privilege solo-teaching. This research seeks to enhance our understanding of team-teaching by examining how two teachers, working in the same classroom at the same time, might or might not contribute to the promotion of inclusive learning. There are well-established policy statements that encourage change and moves towards the use of team-teaching to promote greater inclusion of students with special educational needs in mainstream schools and mainstream classrooms. What is not so well established is the practice of team-teaching in post-primary settings, with little research conducted to date on how it can be initiated and sustained, and a dearth of knowledge on how it impacts upon the students and teachers involved. Research questions and aims. In light of the paucity and inconclusive nature of the research on team-teaching to date (Hattie, 2009), the orientating question in this study asks ‘To what extent, can the introduction of a formal team-teaching initiative enhance the quality of inclusive student learning and teachers’ learning at post-primary level?’ The framing of this question emerges from ongoing political, legal and educational efforts to promote inclusive education. The study has three main aims. The first aim of this study is to gather and represent the voices and experiences of those most closely involved in the introduction of team-teaching; students, teachers, principals and administrators. The second aim is to generate a theory-informed understanding of such collaborative practices and how they may best be implemented in the future. The third aim is to advance our understandings regarding the day-to-day, and moment-to-moment interactions, between teachers and students which enable or inhibit inclusive learning. Sample. In total, 20 team-teaching dyads were formed across seven project schools. The study participants were from two of the seven project schools, Ash and Oak. It involved eight teachers and 53 students, whose age ranged from 12-16 years old, with 4 teachers forming two dyads per school. In Oak there was a class of first years (n=11) with one dyad and a class of transition year students (n=24) with the other dyad. In Ash one class group (n=18) had two dyads. The subjects in which the dyads engaged were English and Mathematics. Method. This research adopted an interpretive paradigm. The duration of the fieldwork was from April 2007 to June 2008. Research methodologies included semi-structured interviews (n=44), classroom observation (n=20), attendance at monthly teacher meetings (n=6), questionnaires and other data gathering practices which included school documentation, assessment findings and joint examination of student work samples (n=4). Results. Team-teaching involves changing normative practices, and involves placing both demands and opportunities before those who occupy classrooms (teachers and students) and before those who determine who should occupy these classrooms (principals and district administrators). This research shows how team-teaching has the potential to promote inclusive learning, and when implemented appropriately, can impact positively upon the learning experiences of both teachers and students. The results are outlined in two chapters. In chapter four, Social Capital Theory is used in framing the data, the change process of bonding, bridging and linking, and in capturing what the collaborative action of team-teaching means, asks and offers teachers; within classes, between classes, between schools and within the wider educational community. In chapter five, Positioning Theory deductively assists in revealing the moment-to-moment, dynamic and inclusive learning opportunities, that are made available to students through team-teaching. In this chapter a number of vignettes are chosen to illustrate such learning opportunities. These two theories help to reveal the counter-narrative that team-teaching offers, regarding how both teachers and students teach and learn. This counter-narrative can extend beyond the field of special education and include alternatives to the manner in which professional development is understood, implemented, and sustained in schools and classrooms. Team-teaching repositions teachers and students to engage with one another in an atmosphere that capitalises upon and builds relational trust and shared cognition. However, as this research study has found, it is wise that the purposes, processes and perceptions of team-teaching are clear to all so that team-teaching can be undertaken by those who are increasingly consciously competent and not merely accidentally adequate. Conclusions. The findings are discussed in the context of the promotion of effective inclusive practices in mainstream settings. I believe that such promotion requires more nuanced understandings of what is being asked of, and offered to, teachers and students. Team-teaching has, and I argue will increasingly have, its place in the repertoire of responses that support effective inclusive learning. To capture and extend such practice requires theoretical frameworks that facilitate iterative journeys between research, policy and practice. Research to date on team-teaching has been too focused on outcomes over short timeframes and not focused enough on the process that is team-teaching. As a consequence team-teaching has been under-used, under-valued, under-theorised and generally not very well understood. Moving from classroom to staff room and district board room, theoretical frameworks used in this research help to travel with, and understand, the initiation, engagement and early consequences of team-teaching within and across the educational landscape. Therefore, conclusions from this study have implications for the triad of research, practice and policy development where efforts to change normative practices can be matched by understandings associated with what it means to try something new/anew, and what it means to say it made a positive difference.

Anglo-Irish relations in the framework of the EEC and Northern Ireland, 1969-1975

This thesis will analyse Anglo-Irish relations between 1969 and 1975, when two topics dominated the relationship: Northern Ireland and the entry of Britain and Ireland into the European Economic Community (hereafter EEC). In 1969 entry to the EEC was still only a possibility and awaited political developments, while the Northern Ireland problem had yet to escalate. 1975 on the other hand confirmed that Ireland would remain in the EEC even if Britain left while Direct Rule for Northern Ireland was confirmed as the British policy for the foreseeable future. These dates are significant because they encompass firstly pre and post entry to the EEC and how this transformed Anglo-Irish relations. Secondly they contain the commencement and then deterioration of the Northern Ireland problem and the attempts to resolve it that finally led to direct rule by Westminster. The study will examine the fluctuating nature of the relationship between Britain and Ireland. Special regard will be devoted to the demands of internal British politics and how such demands affected the relationship. Overall, the study will demonstrate how the bilateral relationship evolved under the pressure of events in Northern Ireland and adapted to the multilateral context of the EEC. It will compare the dynamics of the states’ interactions in two extremely different areas. The thesis will demonstrate how entry to the EEC transformed the unequal Anglo-Irish economic relationship and created one of partners within the EEC. It will also analyse how the developing Northern Ireland problem caused changes to British policy. In particular, it will examine how the British Government came to recognise the beneficial role that the Republic of Ireland might play in resolving the Troubles in Northern Ireland.

Remembrance of the ancestors in contemporary paganism: Lineage, identity, and cultural belonging in the Irish context

This article explores some of the ways of remembering and honouring the ancestors in contemporary Pagan religious traditions, with a focus on the Irish context. An overview is provided of how the "ancestors" are conceptualised within Paganism, as well as where they are believed to be located in the afterlife or Otherworld. Veneration of ancestral peoples is a significant part of many Pagan rituals. Some methods of honouring the dead, and contacting the dead, through ritual practices are described. Remembering and honouring the dead, whether distant forebears or more recent relatives, is particularly important during the Pagan celebration of the festival of Samhain, feast of the dead, on October 31. Issues around ancestors, lineages and ethnicity are significant in many Pagan traditions, and attention is paid to these factors in terms of the Irish Pagan community's sense of cultural belonging as well as their sense of place in a physical respect in relation to the landscape, proximity of sacred sites, and other features of their geographical location.