We present several new results on the combinatorial properties of a locally restricted version of monomino-domino coverings of rectilinear regions. These are monomino-domino tatami coverings, and the restriction is that no four tiles may meet at any point. The global structure that the tatami restriction induces has numerous implications, and provides a powerful tool for solving enumeration problems on tatami coverings. Among these we address the enumeration of coverings of rectangles, with various parameters, and we develop algorithms for exhaustive generation of coverings, in constant amortised time per covering. We also con- sider computational complexity on two fronts; firstly, the structure shows that the space required to store a covering of the rectangle is linear in its longest dimension, and secondly, it is NP-complete to decide whether an arbitrary polyomino can be tatami-covered only with dominoes. / Graduate / 0984 / 0405 / alejandro.erickson@gmail.com

The selective transformation of carbon-carbon and carbon-hydrogen bonds represents an attractive approach and rapidly developing frontier in synthesis. Benefits include step and atom economy, as well as the ubiquitous presence in organic molecules. Advances to this exciting realm of synthesis are described in this thesis with an emphasis on the development of catalytic, selective reactions under mild conditions. Additionally some applications of the methodologies are demonstrated. In Chapter 1, the first examples of inter-and intramolecular enantioselective conjugate alkenylations employing organostannanes are reported. A chiral, cationic Rh(I)-diene complex catalyzed the enantioselective conjugate addition of alkenylstannanes to benzylidene Meldrum’s acids in moderate enantiomeric ratios and yields. Notably, the cationic and anhydrous conditions required for the asymmetric alkenylation are complementary to existing protocols employing other alkenylmetals. In Chapter 2, a domino, one-pot formation of tetracyclic ketones from benzylidene Meldrum’s acids using Sc(OTf)3 via a [1,5]-hydride shift/cyclization/Friedel-Crafts acylation sequence is described. Respectable yields were obtained in accord with the ability to convert to the spiro-intermediate, and considering the formation of three new bonds: one C-H and two C-C bonds. An intriguing carbon-carbon bond cleavage was also serendipitously discovered as part of a competing reaction pathway. In Chapter 3, the pursuit of novel C-H bond transformations led to the development of non-carbonyl-stabilized rhodium carbenoid Csp3-H insertions. This methodology enabled the rapid synthesis of N-fused indolines and related complex heterocycles from N-aziridinylimines. By using a rhodium carboxamidate catalyst, competing processes were minimized and C-H insertions were found to proceed in moderate to high yields. Also disclosed is an expedient total synthesis of (±)-cryptaustoline, a dibenzopyrrocoline alkaloid, which highlights the methodology. In Chapter 4, the Lewis acid promoted substitution of Meldrum’s acid discovered during the course of the domino reaction was explored in detail. The protocol transforms unstrained quaternary and tertiary benzylic Csp3-Csp3 bonds into Csp3-X bonds (X = C, N, H) and has even shown to be advantageous with regards to synthetic utility over the use of alternative leaving groups for substitutions at quaternary benzylic centers. This reaction has a broad scope both in terms of suitable substrates and nucleophiles with good to excellent yields obtained (typically >90%).

Im Rahmen dieser Arbeit wird eine neuartige Deoxygenierungskaskade von Flavanonen bzw. Isoflavanonen via asymmetrischer Transferhydrierung (ATH) beschrieben. Diese Methodik ermöglicht einen einstufigen Zugang zu enantiomerenreinen Flavanen bzw. Isoflavanen aus entsprechenden racemischen Ketonen. Unter Verwendung der ATH-Deoxygenierungskaskade werden hoch enantioselektive Naturstoffsynthesen elaboriert. So erfolgt eine effiziente Darstellung der Flavane Brosimin A, Brosimin B, Brosimacutin L, Kazinol U und 7,3‘-Dihydroxy-4‘-methoxyflavan. Darüber hinaus wird mittels dynamischer kinetischer Racematspaltung die Totalsynthese der Isoflavane Equol, Manuifolin K und Eryzerin D beschrieben.

Nous étudions dans ce mémoire les propriétés des ensembles de pavages engendrés par des jeux de tuiles de Wang exhibant une ou plusieurs directions de déterminisme local, en accordant une importance toute particulière aux jeux déterministes dans les quatre directions diagonales simultanément, dits 4-way déterministes. Après avoir proposé une construction alternative d’un jeu de tuiles apériodique 4-way déterministe, nous étudions plusieurs problèmes de décision sur ces objets et complétons en particulier le résultat d’indécidabilité du problème du pavage dans le cadre 4-way déterministe établi par Lukkarila en montrant l’indécidabilité du problème du pavage périodique 4-way déterministe. Nous montrons également que des familles complexes de coloriages du plan telles que celles engendrées par les substitutions restent sofiques dans un cadre 4-way déterministe. Nous proposons une bi-déterminisation des constructions de jeux de tuiles point-fixe de Durand, Romashchenko et Shen et en tirons quelques premières applications. Enfin, nous considérons l’opportunité d’élargir le rayon de la règle locale de déterminisme afin de limiter les directions d’expansivité et ainsi de permettre la construction localement déterministe de systèmes de particules et collisions non triviaux. Nous introduisons un nouveau modèle syntaxique commode afin de travailler à rayon deux et revisitons des problématiques de Lukkarila dans ce cadre. / In this thesis, we study some properties of the sets of tilings generated by Wang tilesets that exhibit one or more directions of local determinism, focusing in particular on tilesets that are simultaneously deterministic in the four diagonal directions, referred to as 4-way deterministic. After having exposed an alternative construction of a 4-way deterministic aperiodic tileset, we study several decision problems on these objects and complete in particular Lukkarila’s result of undecidability of the Domino Problem in the 4-way deterministic setting proving the undecidability of the 4-way deterministic periodic Domino Problem. We also prove that some complex families of colorings of the plane such that those generated by substitutions remain sofic in the 4-way deterministic setting. We propose a bi-determinization of the constructions by Durand, Romashchenko and Shen of fixed-point tilesets and give some first applications. Finally, we investigate the idea of extending the radius of the local rule of determinism in order to reduce the set of directions of expansiveness and thus allow the local realization of non-trivial particles and collisions systems. We introduce a new and convenient syntactic model to deal with radius two and revisit some of Lukkarila’s problems in this setting.

Nous étudions, dans la première partie de notre thèse, les polysimplexes d’un espace euclidien de dimension quelconque, c’est-à-dire les objets consistant en une juxtaposition de simplexes réguliers (de tétraèdres si la dimension est 3) accolés le long de leurs faces. Nous étudions principalement le groupe des symétries de ces polysimplexes. Nous présentons une façon de représenter un polysimplexe à l’aide d’un diagramme. Ceci fournit une classification complète des polysimplexes à similitude près. De plus, le groupe des symétries se déduit du groupe des automorphismes du diagramme. Il découle en particulier de notre étude qu’en dimension supérieure à 2, une telle structure ne possède jamais deux faces parallèles et ne contient jamais de circuit fermé de simplexes.<p><p>Dans la seconde partie de notre thèse, nous abordons un problème classique de combinatoire :l’énumération des pavages d’un rectangle mxn à l’aide de dominos. Klarner et Pollack ont montré qu’en fixant m la suite obtenue vérifie une relation de récurrence linéaire à coefficients constants. Nous établissons une nouvelle méthode nous permettant d’obtenir la fonction génératrice correspondante et la calculons pour m <= 16, alors qu’elle n’était connue que pour m <= 10.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Palladium-catalysed carbonylative multicomponent reactions have proven useful for the synthesis of structurally diverse compounds. Carbon monoxide serves as an atom-efficient, one-carbon building block, which allows for further structural elaboration of the carbonyl compound. By varying the components of the carbonylative multicomponent reaction, considerable product diversity can readily be attained. However, due to the reluctance to use toxic CO gas, considerable efforts have been directed at exploring non-gaseous approaches. The work described in this thesis has mainly focused on the development of palladium(0)-catalysed, carbonylative multicomponent synthetic methodology, using the non-gaseous CO source molybdenum hexacarbonyl, in the synthesis of heterocycles and other biologically relevant functional groups. The first part of this work describes the development of a non-gaseous carbonylative Sonogashira cross-coupling of bifunctional ortho-iodoanilines and terminal alkynes. Where 4-quinolones were synthesised via a carbonylation/cyclisation sequence. Using a similar synthetic strategy, three different N-cyanobenzamide intermediates were prepared by palladium-catalysed carbonylative couplings of various aryl halides and bromides and cyanamide. The formed intermediates provided a basis for further chemical transformations. First, ortho-iodoanilines were carbonylatively coupled with cyanamide and subsequently cyclised to yield heterocyclic 2-aminoquinazolinones. Next, building on those findings, the same synthetic strategy was applied to ortho-halophenols to provide a highly convenient domino carbonylation/cyclisation method for the preparation of benzoxazinones. The developed method was used to evaluate the efficiency of various non-gaseous CO sources. Third, the palladium-catalysed carbonylative synthesis of N-cyanobenzamides, was used to produce biologically relevant N-acylguanidines with considerable product diversity. Finally, one of the developed carbonylative methodologies was used in the preparation of potential NDH-2 inhibitors based on a quinolinyl pyrimidine scaffold. The prepared compounds were biologically evaluated in terms of inhibition of oxidoreductase NDH-2 and antibacterial activity on Gram-negative bacteria, S. aureus and Mtb. The biological evaluation revealed that some of the quinolinyl pyrimidines exerted inhibitory activity on the NDH-2 enzyme and possessed antibacterial properties. The work described in this thesis has been devoted to the development of non-gaseous one-pot, multicomponent carbonylation/cyclisation and carbonylation/amination reactions. The described methods offer highly attractive synthetic strategies that can be of great value to synthetic and medicinal chemists.

Le squelette indolo[2,3-b]quinoléique est une cible synthétique attrayante car il est présent notamment dans la néocryptolépine, alcaloïde aux propriétés cytotoxiques et antipaludéennes. Nous proposons ici une approche originale pour accéder à ce tétracycle, qui combine dans une réaction radicalaire en cascade une cyclisation à un réarrangement de Smiles. La mise au point des conditions expérimentales et l'étude mécanistique de cette voie ont constitué le premier objectif de ce travail. Outre les produits attendus, les études structurales approfondies ont mis en évidence la formation de composés inédits résultant d'étapes radicalaires supplémentaires. En parallèle, l'application de la méthode à un substrat judicieusement fonctionnalisé a conduit au 3-(2'-aryl-N-alkylacétamido)oxindole, un intermédiaire clé vers le système indolo[2,3-b]quinoléique 6 et 11 disubstitué ciblé. / The indolo[2,3-b]quinoline ring system is an attractive synthetic target present in neocryptolepine, an antiplasmodial and cytotoxic alkaloid. We proposed an original pathway toward this squeleton, combining as key step a 5-exo-trig cyclisation to a Smiles rearrangement in a domino radical process. We first focused on scope and limitations studies and mechanistic investigations. Apart from the cyclised-rearranged products we isolated new original structures resulting from supplementary radical reactions. The application of the developed method to a conveniently functionalised substrate led to 3-(2'-aryl-N-alkylacetamido)indolinone, a key intermediate which was further converted to the aimed 6,11-disubstituted indolo[2,3-b]quinoline tetracycle.

Master´s thesis is considered with design of algorithms for new module of company information system. In the beginning of thesis there are characterized types of ways to describe an information systems. For specification of described system is briefly defined IBM Lotus Notes environment. Next chapter is about object-oriented analysis and design of a module of information system by using UML´s diagrams in modeling tool Enterprise Architect. In the third chapter is made analysis and design of module´s connection with current system, specificly update data in form. Thesis shows designed algorithms in environment of Lotus Domino Designer by using LotusScript and SQL languages and Lotus Domino Connector for access into the database by using ODBC. In last part of thesis is proposed to use a mapping tool to mapp the ITC infrastructure by using Change management process according to ITIL method, to manage all the changes in developing system effectively.

Depuis une quinzaine d’année, le Centre Risque & Performance (CRP) de Polytechnique Montréal a mis en place un outil sociotechnique d'aide à la décision, appelé DOMINO. Essentiellement utilisé à Montréal et Québec, DOMINO a permis d'améliorer efficacement la gestion des infrastructures essentielles interdépendantes (IEI) dans ces villes. Notre étude amorce la réflexion sur l’implantation et l’utilisation de DOMINO dans le contexte d’une métropole de l'Afrique subsaharienne comme Yaoundé. Celle-ci s’appuie sur l’expérience du CRP et soulève des questions liées à son adaptabilité, à sa transférabilité et à son applicabilité. En effet, il s’agit d’une métropole aux caractéristiques urbanistique, socio-économique, politique et technique très différentes de celles du Canada. Dans cette étude, nous avons exploré les problématiques liées à l’interdépendance, autant fonctionnelle que géographique des infrastructures essentielles. Elle nous a permis de faire une caractérisation des parties prenantes et de montrer la nécessité pour celles-ci de créer ou de renforcer la collaboration entre elles, afin d’être en mesure d’utiliser de manière optimale l’outil à implanter. Nous proposons une structure de gouvernance d’un Espace de coopération qui prend en compte les facteurs politiques, institutionnels, culturels, technique et temporel, afin d’assurer l’efficacité des actions mises en œuvre. Une telle étude nous a donné l’occasion de réfléchir sur l’articulation entre la démarche du CRP avec les pratiques de l’urbanisme. Ceci en examinant la fonction de l’Espace de coopération comme espace de coordination des intervenants en milieu urbain et en menant un travail réflexif sur le rôle et le positionnement d’un urbaniste dans une démarche d’implantation d’une technologie numérique. Nous avons répondu à notre question spécifique de recherche qui était de savoir si l’outil DOMINO peut permettre de créer un Espace de coopération regroupant les partenaires publics et privés responsables des infrastructures essentielles interdépendantes de la métropole de Yaoundé ? / For about fifteen years, Montréal Polytechnique Center for Risk & Performance (CRP) has implemented a socio-technical decision support tool called DOMINO. DOMINO has been used extensively in Montreal and Quebec City to effectively improve the management of inter-related critical infrastructure (IEI) in these cities. Our study begins to reflect on the implementation and use of DOMINO in the context of a metropolis in sub-Saharan Africa such as Yaounde. This builds on the experience of the CRP and raises issues related to its adaptability, transferability and applicability. Indeed, it is a metropolis with urbanistic, socio-economic, political and technical characteristics very different from those of Canada. In this study, we explored the issues related to the functional and geographic interdependence of critical infrastructure. It allowed us to characterize the stakeholders and to show the need for them to create or reinforce the collaboration between them, in order to be able to use optimally the tool to implement. We propose a governance structure of an area of cooperation that takes into account the political, institutional, cultural, technical and temporal factors, in order to ensure the effectiveness of the actions implemented. Such a study gave us the opportunity to reflect on the link between the CRP's approach and urban planning practices. This is by examining the function of the cooperation space as a coordination space for urban stakeholders and by carrying out a reflexive work on the role and positioning of an urban planner in the implementation of digital technology. We answered our specific research question, which is to know if the DOMINO tool can help to create a space of cooperation bringing together the public and private partners responsible for the interdependent essential infrastructures of the Yaounde metropolis?

Im Rahmen dieser Arbeit wird eine neuartige Deoxygenierungskaskade von Flavanonen bzw. Isoflavanonen via asymmetrischer Transferhydrierung (ATH) beschrieben. Diese Methodik ermöglicht einen einstufigen Zugang zu enantiomerenreinen Flavanen bzw. Isoflavanen aus entsprechenden racemischen Ketonen. Unter Verwendung der ATH-Deoxygenierungskaskade werden hoch enantioselektive Naturstoffsynthesen elaboriert. So erfolgt eine effiziente Darstellung der Flavane Brosimin A, Brosimin B, Brosimacutin L, Kazinol U und 7,3‘-Dihydroxy-4‘-methoxyflavan. Darüber hinaus wird mittels dynamischer kinetischer Racematspaltung die Totalsynthese der Isoflavane Equol, Manuifolin K und Eryzerin D beschrieben.