Metal-mediated intramolecular hydroamination and hydro(acy)alkoxylation reactions

This PhD thesis describes work undertaken to effect asymmetric catalysis in hydroamination and hydro(acy)alkoxylation reactions of allenes. The introductory Chapter provides an overview of recent advances in asymmetric heterofunctionalisation reactions of allenes. This includes intra- and inter-molecular reactions involving C-N and C-O bond formations. Chapter 2 begins by comparing the preparation of a γ-allenic alcohol by two different synthetic routes and its subsequent use in intramolecular hydroalkoxylation reactions using copper(II) and silver(I) salts. From this study, the ability of silver diphosphine complexes to facilitate enantioselective hydroalkoxylation reactions in a 5-exo-trig fashion was discovered. Extensive reaction optimisation was undertaken, however only moderate ee’s and conversions were observed. In Chapter 3, the use of other metal Lewis acids to catalyse hydroalkoxylation reactions of γ-allenic alcohols is presented. DFT calculations undertaken by a colleague (Prof H. S. Rzepa) were used to rationalise the observed regioselectivities with silver(I), zinc(II), and tin(II) triflates. From DFT calculations, the metal counteranion was found to be intimately involved in the C-O bond formation. In the following two Chapters, the possibility of asymmetric synthesis by using chiral anionic ligands is discussed. In Chapter 4, additional γ-allenic alcohols and β-allenic acids were synthesised for intramolecular hydroalkoxylation or hydroacyalkoxylation reactions respectively. In Chapter 5, the respective γ-allenic amines were prepared for intramolecular hydroamination. In both cases, the outcome, scope and limitations of the reaction are discussed. In Chapter 6, an overall conclusion and future work is discussed. The last Chapter contains experimental procedures and characterisation data of all the compounds synthesised during the course of this project

Spouse Abuse

The term spouse abuse is commonly used to refer to Aggressive, violent and/or controlling behaviours that take place between two people involved in an intimate Relationship. Spouse abuse is a high frequency crime resulting in victims from all social classes, ethnicities, genders and educational backgrounds. Preventative methods at societal and community levels are required in addition to more traditional intervention approaches in order to adequately address this problem. This entry will provide an evidence based description of spouse abuse, considering its definition, terminology, prevalence, victims and Perpetrators and issues related to the treatment and prevention of this problem

The Word Becomes Flesh

(Excerpt) Mrs. Gahr, my teacher for several years in the one-roomed country school I attended, always said a word is really yours when you have used it correctly in a sentence three times. There is a sense in which we can say the living Word becomes ours when we use it Using the living word, however, is not just putting nouns and verbs and other parts of speech together. Using the living word correctly is not even just rightly dividing law and gospel. Using the living word must also involve actions and deeds. One of the ways the church uses the word correctly is what we have often called diakonia. Through its service within the community of faith and for the world, the church uses the word, making it flesh in the lives of people. And .as we use the word that way, we may well find that the word becomes not only flesh but also really ours