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Synthèse d'hétérocycles azotés et oxygénés par catalyse acide et oxydation aodique.Moreau, J. 23 October 2009 (has links) (PDF)
La catalyse acide pour la synthèse de structures hétérocycliques à visée thérapeutique est un outil puissant qui présente des avantages économiques certains. Nous décrivons ici la synthèse de 1,4-dihydropyridines non symétriques catalysée selon différentes approches, à partir d'aldéhydes -insaturés et de -énaminoesters. La synthèse de catalyseurs chiraux a ensuite permis l'obtention de ces molécules de manière énantiosélective. L'extension de cette réaction à des -cétoesters et -énaminones cycliques a également conduit à la formation de 2H-chroménones et tétrahydroquinolinones de manière régiosélective. Une seconde partie de ce mémoire traite de la synthèse de deux alcaloïdes naturels, la (R)-Crispine A et la (R)-Bernumicine, via l'utilisation d'-aminonitriles précurseurs, préparés par cyanation anodique. Utilisés dans une séquence diastéréosélective d'alkylation-réduction, ces derniers ont permis l'obtention des composés finaux avec des excès énantiomériques supérieurs à 90%.
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Part I: Synthesis of Aromatic Polyketones Via Soluble Precursors Derived from Bis(A-Amininitrile)S; Part Ii: Modifications of Epoxy Resins with Functional Hyperbranched Poly(Arylene Ester)sYang, Jinlian III 24 April 1998 (has links)
Part I: This part of the dissertation describes a new approach to high molecular weight aromatic polyketones via soluble precursors derived from bis(a-aminonitrile)s. Bis(a-aminonitrile)s were easily synthesized from dialdehydes and secondary amines in very high yield by the Strecker reaction. Polymerization of bis(a-aminonitrile)s with activated dihalides using NaH as base in DMF yielded soluble, high molecular weight polyaminonitriles, which were hydrolyzed in acidic conditions to produce the corresponding polyketones. A novel approach to the synthesis of high molecular weight wholly aromatic polyketones without ether linkages or alkyl substituents in the polymeric backbones was demonstrated. These polyketones displayed excellent thermal properties and solvent resistance. A very efficient synthesis for diphenol and activated dihalide monomers containing keto groups was also developed based on a-aminonitrile chemistry. Novel activated dihalide monomers were obtained in quantitative yields. This method is suitable for any activated dihalide by reaction with 2 equivalents of 4-fluorobenzylaminonitrile and NaH, followed by hydrolysis to produce a new monomer with two more p-fluorobenzoyl units. For the synthesis of polyaminonitriles containing ether linkages in the polymeric backbone, only low to medium molecular weight polymers were obtained. The model studies proved that the carbanions of the aminonitriles can react with ether linkages to form more stable phenoxide anions and cause the termination of the polymerization.
Part II: Functional hyperbranched poly(arylene ester)s were synthesized by thermal polymerization of 5-acetoxyisophthalic acid or 3,5-diacetoxybenzoic acid. Carboxylic terminated hyperbranched copolyesters were also synthesized by copolymerization of 5-acetoxyisophthalic acid and 3-hydroxybenzoic acid using different molar ratios of these two monomers. Both carboxylic acid and phenolic terminated hyperbranched polyesters were functionalized with different reactive groups. The carboxyl terminated hyperbranched poly(arylene ester)s were successfully used to modify inherently brittle epoxy resins. The hyperbranched polymers were chemically incorporated into the epoxy networks using triphenylphosphine (TPP) as a catalyst and 4,4'-diaminodiphenyl sulfone (DDS) as a curing agent. The chemistry and the proper formation of crosslinked networks were confirmed by solution 1H NMR, solid state CPMAS 13C NMR, kinetic FTIR spectroscopes and gel fraction analysis. Fracture toughness was improved without sacrificing thermal properties. The fracture toughness K1C values of the modified epoxies were found to be a function of the percentage loading, the molecular weights and the proportion of linear units of hyperbranched polyesters. Because the carboxylic acid terminated hyperbranched poly(arylene ester)s were immiscible with the commercially available epoxy EPON 828, the percentage loadings of hyperbranched modifiers were limited and the processibility of epoxy resins was difficult, especially at high percentage loadings of hyperbranched modifiers. These problems could be solved using phenolic terminated hyperbranched poly(arylene ester)s, which are more soluble in epoxy resins. / Ph. D.
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Dynamic Covalent Resolution: Applications in System Screening and Asymmetric SynthesisVongvilai, Pornrapee January 2009 (has links)
Combined thermodynamic/kinetic events amount to a kinetically controlled Dynamic Combinatorial Resolution (DCR) process, where the lability of themolecules/aggregates are used to generate dynamics, and the species experiencing the lowest activation energy is selected via kinetic process. Bothinter- and intramolecular processes can be performed using this concept,resulting in complete resolution and associated amplification of the selected species. When intermolecular processes are resolved using this method, an additional advantage is that only a catalytic amount of selector is required tocontrol the system.In this thesis, the Henry and Strecker reactions were developed as efficient C–C bond-forming routes to single and multi-level dynamic covalent systems.These methods efficiently provided a vast variety of substrates from smallnumbers of starting compounds. These dynamic systems, generated underthermodynamic control at mild conditions, were coupled in one-pot processes with kinetically controlled lipase-mediated transacylation. The enzym emediated resolution of the dynamic nitroaldol system led to enantiomericallypure β-nitroacetates in high yield. Furthermore, combination of multi-leveldynamic Strecker systems and lipase-mediated acylation resulted in theresolution of specific α-aminonitriles from the pool.In addition, the asymmetric synthesis of discrete β-nitroalkanol derivatives wassimply achieved, resulting in high yields and high enantiomeric purities through the direct one-pot procedure. Moreover, racemase type activity oflipase enzyme through N-substituted α-aminonitrile structure has been discovered. By use of control experiments together with molecular modeling,the mechanism of the racemization process has been established. Asymmetric synthesis of N-methyl α-aminonitriles was also performed through the dualfunction of lipase, resulting in high yield and good enantio selectivity. / <p>QC 20100818</p>
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Metal-Mediated And Metal-Free Organic Transformations : C-H Functionalization Of Tertiary Amines, Synthesis Of Carbonyl Compounds And Ring-Opening Of AziridinesAlagiri, K 12 1900 (has links) (PDF)
No description available.
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