Les jasmonates de méthyle sont des oxylipines asymétriques impliquées dans les mécanismes de défense, de développement et de régulation des organismes photosynthétiques terrestres ou marins face à des stress biotiques et abiotiques. Parmi les quatre stéréoisomères, seuls l'épi-jasmonate et l'ent-épi-jasmonate de méthyle possèdent de bonnes propriétés organoleptiques mais aussi une forte activité phytohormonale permettant l'élicitation de métabolites secondaires bioactifs. En ciblant spécifiquement une hexokinase mitochondriale régulant le métabolisme des cellules cancéreuses, les jasmonates de méthyle constituent d'excellents candidats pour de nouveaux agents thérapeutiques. Dans la recherche constante de nouvelles molécules thérapeutiques issues du milieu naturel, notre laboratoire s'est donc focalisé sur la synthèse énantiosélective de l'épi-jasmonate et l'ent-épi-jasmonate de méthyle, au départ de diols bicycliques homochiraux monoprotégés dérivant du cyclooct-1,5-diène.Afin d'obtenir ces diols bicycliques énantiopurs, une stratégie innovante a consisté en l'étude de la réaction d'électrocyclisation du méso-époxyde dérivé du cyclooct-1,5-diène assistée par des ligands chiraux métallés diversement fonctionnalisés, les catalyseurs de Jacobsen. En mettant à profit notre savoir-faire sur les désymétrisations enzymatiques, une stratégie parallèle optant pour la résolution énantiosélective de diols homochiraux monocycliques, ou de diols bicycliques C2-symétriques nous a permis d'accéder à des silanyloxyindèn-5-ones chirales, précurseurs clé des cis-jasmonates de méthyle énantiopurs. Enfin, la synthèse racémique de deux jasmonoïdes clé, la (±)--jasmolactone, puis le (±)-épi-jasmonate de méthyle a été validée en 15 étapes à partir du cyclooct-1,5-diène.

A busca por materiais derivados de fontes renováveis e com características como biocompatibilidade e biodegradabilidade tem crescido significativamente nos últimos anos. A utilização de enzimas na polimerização representa um grande passo para a obtenção destes, visto que possibilitam a produção de polímeros evitando a utilização de catalisadores tóxicos e, assim, melhorando sua biocompatibilidade. O presente trabalho descreve a utilização de monômeros funcionais derivados de fontes renováveis na produção de poliésteres hidrolisáveis via catálise enzimática. As sínteses de polímeros produzidos a partir de isosorbídeo e ácidos dicarboxílicos ou derivados - como seus ésteres alquílicos e vinílicos - foram feitas utilizando a lipase de Candida antarctica Fração B como catalisador. As polimerizações foram realizadas por policondensações em massa e em solução, utilizando-se diferentes solventes e diferentes técnicas para remoção de subprodutos de reação. A principal abordagem foi o estudo das diferentes condições reacionais realizadas, variando-se o tempo de reação, tipo do monômero, solvente utilizado (se for o caso) e tipo de técnica para remoção de subprodutos visando o aumento da massa molar dos polímeros. A condição que forneceu os materiais com maiores massas molares foi a policondensação em solução, utilizando a mistura cicloexano:benzeno como solvente. Tendo por objetivo investigar profundamente a condição ótima obtida, e estabelecer padrões de comparação com outros sistemas, foram estudados, nessa condição, parâmetros como tempo de reação, efeito do tamanho da cadeia carbônica do monômero, grupo de saída, solubilidade dos polímeros e diluição do sistema. Os materiais obtidos foram caracterizados por cromatografia por exclusão de tamanho (SEC), termogravimetria (TG), calorimetria exploratória diferencial (DSC), espectroscopia no infravermelho, difração de raios-X, e Ressonância Magnética Nuclear (RMN) de 1H e 13C. Através deste trabalho foi provado que, embora apresente uma cinética de reação lenta, a polimerização enzimática deste diol secundário estericamente impedido é possível, fornecendo poliésteres com massas molares similares às obtidas via catálise química. Todos os resultados obtidos neste trabalho são inéditos no que diz respeito à polimerização enzimática de dióis secundários impedidos, mais especificamente de isosorbídeo. / The search for materials derived from renewable sources, with characteristics such as biocompatibility and biodegradability has grown significantly in recent years. The use of enzymes in the polymerization is a major step for the attainment of these materials, since it allows the production of polymers while avoiding the use of toxic catalysts and thus improving its biocompatibility. This paper describes the use of functional monomers derived from renewable sources in the production of hydrolysable polyesters by enzyme catalysis The synthesis and characterization of polymers derived from isosorbide and dicarboxilic acids or derivatives - such as alkyl and vinyl esters - were carried out using the lipase from Candida antarctica - Fraction B as catalyst. The polymerizations were accomplished by polycondensations in bulk and in solution, using different solvents and different techniques for removal of reaction byproducts. The main approach was to study the different reaction conditions, by varying the reaction time, monomer type, solvent used (if applicable) and the type of technique for removal of byproducts, aiming at maximizing polymer molar mass. The condition that provided the material with higher molecular weight was the solution step-growth polymerization, using a mixture cyclohexane:benzene as solvents. Aiming to thoroughly investigate the optimum condition obtained, and to establish standards for comparison with other systems, it was studied, in this condition, parameters such as reaction time, effect of monomer carbon chain length , leaving group, polymers solubility of and dilution of the reaction system. The materials were characterized by gel permeation chromatography (SEC), thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy, X-ray diffraction and 1H and 13C Nuclear Magnetic Resonance (NMR). Through this work it was proved that, in spite of a slow reaction kinetics, the enzymatic polymerization of this hindered secondary diol is possible, providing polyester with molecular weight similar to those obtained by chemical catalysis. All results obtained in this work are unprecedented with respect to the enzymatic polymerization of hindered secondary diols, more specifically of Isosorbide.

This work deals with the design and synthesis of building blocks, usable for creating dynamic polymers based on the reversible formation of hemiacetals bond. Next part is focused on the study of the formation of hemiacetal between polyfunctional alcohols and trifluoromethylketones via NMR spectroscopy. Key words: constitutional dynamic chemistry, hemiacetals, trifluoromethylketones, diols and polyols

No description available.

The homoaldol reaction is one of the most powerful methods for the construction of C–C bonds as well as 1,4-oxygenated compounds yet this reaction remains in challenging tasks due to the instability of homoenolates which spontaneously cyclize to the cyclopropanolate. A regioselective catalytic homoaldol equivalent reaction of 3-bromo vinyl acetate with aldehydes under Cr(III)-Mn(0) redox condition was developed. This homoaldol equivalent reaction allows access to the 1,4-oxygenated compounds that are not possible by a conventional aldol process. Mild hydrolysis of the vinyl acetate and reduction of the homoaldol adducts generated diols and lactols in high yield (99%). Further manipulation including stereoselective epoxidation and cyclopropanation was achieved in an efficient manner. Furans, found in many natural products and utilized in drug discovery, have been well studied but current synthetic methods toward furans have some limitations in functional group tolerance, substrate scope, and low product yield in many cases. A highly efficient and catalytic cycloisomerization reaction that transforms acetylenic α,β-epoxides to 2,3,5-tri-substituted furans under InCl3 catalysis was developed. This reaction sequence allows access to rapid construction of highly valuable, tri-substituted furan derivatives. Cross-coupling reactions utilizing transition metals and Lewis acids are important synthetic tools for the formation of C–C and C–N bonds and a number of cross-coupling reactions between α-bromo carbonyl compounds and metal reagents such as aryl metals, alkenyl metals, and alkyl metals have been reported. Transition metal-catalyzed cross-coupling reaction for the construction of α-alkynyl carbonyl compounds has reported in a limited case. The first approach to secondary α-alkynyl carbonyl compounds from secondary α-bromo esters and amides with tributyl(phenylethynyl)stannane under palladium-catalyzed cross-coupling reaction conditions was developed. This synthetic method allows access to secondary α-alkynyl carbonyl compounds which are valuable precursors in pharmaceuticals and agricultural applications.