Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Drastic alterations to the North American Southwest’s hydrology have highly influenced resident fish communities. In New Mexico and Texas, the Pecos River has been severely altered as a result of water manipulation, isolating backwaters and various habitats that were once connected to the main river. Cyprinodon pecosensis (Pecos pupfish) has been highly impacted due to the effects of anthropogenic water manipulation, as well as species introductions. Cyprinodon pecosensis populations have become isolated and scattered, residing in sinkholes, remnant lakes, and static backwaters, thus creating numerous micropopulations. The purpose of this study was to assess the morphological variation in cranial features that occur in response to varied habitats, especially in terms of environmental factors and species co-occurrence. Landmark-based geometric morphometrics was used to assess shape variation across the aforementioned micropopulations comprising four general habitat types and 27 different localities, each with varied community structure and salinity. Results from this study suggest that head and mandible morphology vary temporally, with year to year variation, as well as among different localities. The head morphology of C. pecosensis was most heavily influenced by habitat type and localities within habitat types, but was largely canalized with the exception of localities classified as deep sinkholes. Year to year variation and localities among habitat types were the most influential factors associated with mandible morphology, but there was strong overlap among the convex hulls that defined regions of morphospace for habitat types. As C. pecosensis is a threatened species, this research has important implications for future conservation and management. Additionally, these results could further aid in the understanding of preserving species in fragmented landscapes.

The destruction and fragmentation of natural habitat is the leading driver of the current extinction crisis. As a result, a research area has emerged focused on studying ecology in islands of natural habitat surrounded by a sea of anthropogenic land uses, so called ‘habitat islands’. However, this research has largely been undertaken on small-medium scales, generally in single systems. Furthermore, many habitat island studies have used previous results and theory derived in the context of oceanic island research. Thus, this thesis aims to examine a variety of macroecological and biogeographical patterns using a large number of purely habitat datasets sourced from both the literature and my own sampling, with the objective of teasing out any general statistical patterns. The various macroecological and biogeographical patterns can be grouped under four broad headings: 1) species–area relationships (SAR), 2) nestedness, 3) species abundance distributions (SADs), and 4) species incidence functions (function of area). Overall, it was found that there were few hard macroecological generalities that hold in all cases across habitat island systems. This is because most habitat island systems are highly disturbed environments, with a variety of confounding variables and undesirable species (e.g. species associated with human land uses) acting to modulate the patterns of interest. Nonetheless, some clear patterns did emerge. In particular, it was found that the power model was by the far the best general SAR model for habitat islands. The slope of the island species–area relationship (ISAR) was related to the matrix type surrounding archipelagos, such that habitat island ISARs were shallower than true island ISARs. Significant compositional and functional nestedness was rare in habitat island datasets, although island area was seemingly responsible for what nestedness was observed. Species abundance distribution models were found to provide useful information for conservation in fragmented landscape, but the presence of undesirable species substantially affected the shape of the SAD. Species incidence function curves were found to vary across space for a given species, but not in any systematic manner. In conclusion, this thesis finds that the application of standard island biogeography theory to habitat islands is too simplistic. It is hoped that the results of this thesis will act as a catalyst for a more macroecological approach to habitat island research, and a starting point for the development of an integrated theory of habitat islands.

Dans ce mémoire, il sera question de la formation de dérivés pipéridines en utilisant la fragmentation de Grob. Tout d’abord, une introduction sur les alcaloïdes ainsi que sur l’expertise du groupe Charette associée à leur formation démontrera l’importance de ces composés dans le domaine de la chimie organique. Cela sera suivi par un résumé de la fragmentation de Grob incluant les conditions de réactions utilisées, l’importance de la structure de la molécule initiale, les prérequis stéréoélectroniques ainsi que les modifications qui y ont été apportées. Le chapitre 2 sera dédié au développement de la méthodologie c’est-à-dire, à l’optimisation de tous les paramètres jouant un rôle dans la fragmentation de Grob. Par la suite, l’étendue de la réaction ainsi que des explications sur la régiosélectivité et la diastéréosélectivité de la réaction seront fournies. La méthodologie peut être exploitée dans un contexte de synthèse qui sera démontré dans le chapitre 3. De plus, elle servira pour une étude mécanistique qui est encore d’actualité à partir du concept d’effet frangomérique. Finalement, quelques projets futurs, notamment des améliorations possibles de la méthodologie, seront présentés dans le dernier chapitre. Le tout sera suivi d’une conclusion résumant l’ensemble des travaux effectués. / This thesis discusses the formation of piperidine derivatives using the Grob fragmentation. Firstly, an introduction of the important alkaloid family as well as previous work completed by the Charette group towards the synthesis of these compounds will be demonstrated. This will be followed by a summary of the Grob fragmentation including a discussion of the reaction conditions, molecular structures, stereoelectronic requirements and modifications of the Grob fragmentation. Chapter 2 will be dedicated to the development of the methodology and more precisely, to the optimization of all parameters necessary to the reaction. Furthermore, the scope of the reaction and some explanation of the regioselectivity and the diastereoselectivity of the reaction will be discussed. The developed methodology can be used in a total synthesis and will be demonstrated in Chapter 3. Moreover, using the frangomeric effect concept, a mechanistic study on the Grob fragmentation will be discussed. Finally, some future projects, especially possible improvement of the methodology, will be presented in the last chapter. This is followed by a conclusion and a summary of the work completed on this project.

Edible potatoes originated in the Andes and were brought to Europe in the 16th century. Their introduction spurred both the European population growth and economic development. Being the world's fourth-largest food crop, potatoes continue to shape the global economy and world history. Glycoalkaloids are natural insect deterrents generated by potatoes, and are known for their toxic effects as well as potential medicinal utilities. Demissidine, the aglycone of the primary glycoalkaloids, represents one major Solanum alkaloid. Its unique indolizidine framework presents a challenging synthetic target in organic chemistry. Our synthesis of demissidine starts from readily available epiandrosterone and takes advantage of a Lewis acid-mediated fragmentation of a γ-silyloxy-β-hydroxy-α-diazoester; the D-ring of a diazo ester derivative of epiandrosterone was efficiently ruptured to provide an aldehyde tethered ynoate product. In combination with a subsequent azomethine ylide 1,3-dipolar cycloaddition and a transition metal catalyzed oxidation/reduction, the core indolizidine framework of demissidine was successfully prepared in a stereoselective manner. In addition, the syntheses of two amino acids, 5-methylenepipecolic acid and (5S)-5-methylpipecolic acid were explored; they are used for the installation of the α-oriented C25 methyl group on demissidine. The successful preparation of demissidine was supported by NMR analysis of the synthetic compound in comparison with a natural sample. As an efficient and stereoselective synthesis, our efforts toward demissidine illuminate a strategy to indolizidine frameworks that could be applied in the preparation of other polycyclic amine natural products.

The fragmentation of γ-silyloxy-β-hydroxy-α-diazoesters to provide tethered aldehyde ynoates was discovered and developed in Prof. Brewer's laboratory. This reaction is a Lewis acid mediated heterolytic cleavage of the Cβ-γ bond of a γ-silyloxy-β-hydroxy-α-diazocarbonyl functional group array contained in a ring compound. This dissertation describes a further study of this ring fragmentation reaction and application of this fragmentation to the preparation of synthetically useful organic molecules. The purpose of this dissertation work was three fold. The first objective was to extend this ring fragmentation reaction to the synthesis of tethered aldehyde ynones by fragmenting various γ-silyloxy-β-hydroxy-α-diazo ketone compounds. The second objective was to develop a new way to make medium size rings by fragmenting fused bicyclic γ-silyloxy-β-hydroxy-α-diazo ketones. The final goal was to use this reaction to make medium size ynolides by fragmentation of fused bicyclic γ-silyloxy-β-hydroxy-α-diazo esters to provide core structures for medium-size lactones which are synthetically challenging to make using other available methods.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.