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

De Budapest à Kaboul via Prague : l’esprit de suite de l’internationalisme socialiste

It is a well-established principle of international law that the threat or use of force against the territorial integrity or political independence of any State is forbidden. It is also recognized that every State has the sovereign and inalienable right to choose its economic System as well as its political social and cultural Systems in accordance with the will of its people, without outside interference, coercion or threat in any form whatsoever. But international law does not prohibit the use of force in the exercice of the right of self-defence if an armed attack occurs and some writers state that there is no rule of international law which forbids the government of one state from rendering assistance to the government of another state.This article is primarily concerned with legal issues related to soviet invasion of Afghanistan; its purpose is to examine official statements put forward in Moscow in order to justify the legality of this armed intervention. As will be seen, there is a perfect similarity between legal arguments used in 1956, 1968 and 1980; this is being done in order to give the domestic crisis an international colouring and to justify a demand for foreign intervention. It must be noted that Soviet troops are "not interfering" in the international affairs of Afghanistan: on the contrary, they are "fighting for" the principle of socialist self-determination of the people of Afghanistan... By definition a war conducted by the USSR is a just and defensive war..

Aspects juridiques de la crise américano-iranienne

From the first day the American Embassy was invaded and its diplomatic staff was seized as hostages by Iran, the United States of America has pursued every legal channel in order to resolve this crisis by peaceful means. Its efforts started with the immediate dispatch of Mr. Ramsey Clark on a mission to negotiate with the government of Iran and were continued in the United Nations through the Secretary General, the Security Council, the U.N. Commission of Inquiry and the World Court. Though one can say that all disputes may theoretically be capable of settlement according to rules of law, it should also be said, as a matter of fact, that international law often has only limited relevance to disputes arising among States. This is so because international legal rules operate within a system which has no general scheme of sanctions and no central organ for the enforcement of international legal rights. States have traditionally utilized coercitive measures short of war in attempting to prevail in disputes with other States. Does this authorize a State to intervene by the use of force for the protection of its nationals abroad ? Even though, from the standpoint of morality, the abortive U.S. rescue operation in Iran may have had sound justifications, any legal justifications that could be put up had to give way before the principle of territorial sovereignty

Pouvoirs discrétionnaires et contrôles ex post facto par les juges : entre justice procédurale et compétence de l’avocat

Au Québec, la justice procédurale contemporaine évoque une approche pragmatique relativement à l’administration de la justice et dans l’interprétation des règles de droit positif, laquelle se matérialise par un accroissement des pouvoirs discrétionnaires dévolus aux juges par le législateur, doublée d’une protection majorée des droits individuels. Cette tendance s’observe en outre à travers l’arrêt Carignan c. La Reine, lequel illustre l’incidence de pouvoirs discrétionnaires et l’exercice de droits fondamentaux sur l’autonomie professionnelle et la compétence des avocats. En matière civile, l’équilibre entre le principe de la stabilité des jugements et l’intérêt de chaque justiciable à voir le litige particularisé à sa situation est tributaire d’une certaine souplesse dans l’application des règles de procédure. Ces observations posent la problématique de la réévaluation des paramètres de la compétence des avocats devant les tribunaux au regard d’une justice procédurale de « seconde modernité ».In Québec, contemporary procedural justice evokes a pragmatic approach to the administration of justice and the interpretation of substantive law, which is materialized by an increase in the discretionary powers vested in judges by the legislator, and further amplified by greater protection of individual rights. This trend is observable in the case of Carignan vs. R., which illustrate the impact of discretionary powers and the exercising of fundamental rights on the professional autonomy and competence of attorneys. In civil matters, the state of equilibrium between the stability of judgments and justiciable interests of anyone appearing in court to see the proceedings adapted to his or her situation depends upon the degree of flexibility in how the rules of procedure are applied. These observations raise the issue of re-evaluating the parameters of attorneys’ competence before the courts as regards procedural justice in an era of « second modernism »

Réflexions portant sur le contrôle de la compétence professionnelle des membres du Barreau du Québec

Devant le faible nombre de décisions jurisprudentielles publiées qui proviennent du Comité de discipline du Barreau du Québec et qui portent sur la compétence professionnelle de ses membres, l'auteure examine le rôle du Barreau dans sa fonction autorégulatrice. Elle propose que, afin de conserver sa légitimité aux yeux du public, celui-ci envisage notamment d'autoriser officiellement la pratique des avocats au sein des cabinets multidisciplinaires et reconnaisse leur spécialisation de facto. Ces mesures s'avèrent nécessaires, puisque les nouvelles variables qui influent sur la pratique du droit découlent d'une conception néo-libérale de la relation entre le professionnel et son client. L'autorégulation doit donc asseoir sa légitimité sur des bases renouvelées, qui refléteront les attentes des clients.Considering how the Disciplinary Committee of the Québec Bar Association has published so few binding decisions regarding members' professional skills, the author examines the role played by the Association in performing its self-regulatory duties. To preserve the Association's legitimacy in the eyes of the general public, she proposes, among other things, that it officially authorize lawyers' practice in multidisciplinary firms and recognize their specialty. Such measures are proving to be necessary owing to new variables impacting the practice of law issuing from a neo-liberal conception of the relation between the professional and his or her client. Self-regulation must therefore base its legitimacy on renewed premises, which will reflect clients expectations