No description available.

No description available.

The initial purpose of this study was to determine if steric problems would account for the difference in the products obtained in the reaction of the N-(substituted)phthalimide with low and high molecular weight amines.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal. / Nous avons exploré et exploité un nouveau type d'addition de Michael des nitroalcanes pour la synthèse des pipéridines et pipéridinones diversifiés, substitués par des aminés et des alcools. Nous avons démontré l'efficacité et la facilité de l'addition conjuguée des nitroalcanes aux amides cycliques a,P-insaturés, et étudié la stéréosélectivité de l'addition. A l'aide de cette réaction, nous avons généré une série de pipéridinones diversifiées, des acides a-aminés, des nitrocyclopropanes et une nouvelle classe de pipéridines substituées par des amines et des alcools. Finalement, nous avons développé une méthode simple et efficace pour l'addition conjuguée des nitroalcanes afin d'obtenir des alkylamines substituées. / The goal of this study was to synthesize novel piperidine and piperidinones with aminomethyl and hydroxymethyl appendages, to be used as probes, scaffolds or mimics. We have demonstrated the efficiency and practicality of nitroalkane conjugate Michael addition to a,p-unsaturated lactams while studying the effects of different nitroalkane substitutents on the stereoselectivity. The noteworthy features of this approach are its operational simplicity, the efficiency of the nitroalkane conjugate addition, and the facile preparation of 2- and 4-substituted 6-oxo-piperidinones.

The invention of catalytic processes that convert feedstock chemicals into pharmacologically-privileged amines is a landmark challenge in organic synthesis. This thesis describes the development of three novel transition-metal catalyzed processes for the synthesis of alkylamines that attempts to meet this challenge. The first Pd-catalyzed methylene β-C−H carbonylation of alkylamines to form substituted β-lactams is reported. Through the synergistic use of a Pd-catalyst and Xanpthos ligand, secondary amines underwent exclusive methylene β-C−H activation in high yields and diastereoselectivities. Subsequently, the development of a remarkably selective methylene β-C−H carbonylation of α-tertiary amines (ATAs), is detailed. This methodology enables the C−H carbonylation of methylene C−H bonds over traditionally more reactive methyl and C(sp2)−H bonds. Importantly, a range of functional groups previously incompatible with C−H technologies were tolerated in good yields. Finally, the development of a novel multicomponent synthesis of tertiary amines is described. The novel photocatalytic single-electron reduction of alkyl iminium ions furnishes -amino radicals that engage alkenes forming a new C-C bond. The reaction exhibits broad functional group tolerance and enables the synthesis of amines not readily accessible by existing methods.