Quando o tetrafluoroborato de N-(α-carbometoximetil)-2,4,6-trifenilpiridínio (Ia) foi tratado com hidróxido de potássio em etanol, resultou uma betaína que, ao ser aquecida na presença de benzaldeído ou p-clorobenzaldeído, não produziu a esperada oxazolidina IIa. Em lugar desta 1,2-di-hidropiridina, formou-se um sal cujo cátion correspondia à estrutura de um N-metil-2,4,6-trifenilpiridínio (III). Este composto resultaria da protonação da ilida intermediária, formada pela descarboxilação da betaína. Porém, quando o mesmo tipo de reação foi efetuada com o derivado α-metilado Ib, o espectro de RMN de H do produto bruto indicou a formação da di-hidropiridina (IIb), na forma de 4 estereoisômeros. A oxazolidina IIa, como um isômero largamente majoritário, pôde ser obtida pela reação do tetrafluoroborato de N-metil-2,4,6-trifenilpiridínio (III) com p-clorobenzaldeído, na presença de uma solução diluída de álcali. Esta oxazolidina era bastante instável e não pode ser purificada, sendo submetida na forma bruta à reação de Diels-Alder com a N-metil-maleimida. Esta reação conduziu a dois adutos isoméricos (IV e V). Embora o aduto majoritário (V) fosse estável em solução de deutero-clorofórmio, o aduto minoritário (IV), na presença desse solvente e à temperatura ambiente, isomerizava-se após algumas horas. A estrutura dos três adutos foi determinada por experimentos de RMN de H (NOESY e NOE 1D seletivo). A adição de um pequeno volume de solução diluída de ácido clorídrico aos compostos IV e V, dissolvidos em acetonitrila e à temperatura ambiente, resultou na isomerização catalítica desses adutos. Porém, quando esta reação de protonação foi efetuada sob refluxo de acetonitrila, formaram-se dois produtos (VI e VII), cuja estrutura era compatível com ocorrência de uma reação de retro-aza Diels-Alder. Finalmente, foi estudado o equilíbrio conformacional de dois novos sais de 2,4,6-trifenil- piridínio, e os resultados foram comparados com aqueles obtidos para os sais análogos 2,4,6-trimetil-substituídos. / When the tetrafluoroborate of N-(α-carbomethoxymethyl)-2,4,6-triphenylpridinium (Ia) was submitted to alkaline hydrolysis followed by decarboxylation upon heating, the resulting betaine failed to undergo the aldol addition reaction with aromatic aldehydes leading, in lieu of the expected oxazolidine (IIa),a salt bearing the cation N-methyl-2,4,6-triphenylpyridinium (III), as a result of the easy protonation of the intermediate ylide. However, for the corresponding a-methylated salt (Ib), the formation of four stereoisomeric 1,2- dihydropiridines was confirmed by inspection of the H NMR of the crude product. As an alternative to this method for obtaining IIa, a mixture of III and p-chlorobenzaldehyde was stirred at room temperature for several hours, in the presence of a diluted aqueous alkali. The resulting 1,2-dihidropyridine (IIa) was rather unstable precluding its isolation from the crude product mixture, and was submitted, without further purification, to the Diels-Alder reaction with Nmethylmaleimide, leading to two diastereomeric isoquinuclidines (IV) and (V). Although the major isomer showed to be stable in a deuterochloroform solution, the minor isomer (IV) underwent a spontaneous isomerization, upon standing in such solvent at room temperature. The stereochemical features of these three aducts could be accessed by NOESY and 1D NOE selective H NMR experiments. By treating a solution of adducts IV and V in acetonitrile with a small volume of aqueous HCl, at room temperature, an acid catalyzed isomerization took place. However, when the protonation reaction of the major diastereoisomer (V) was performed in acetonitrile at the reflux temperature, two products (VI and VII) were isolated, highlighting the occurrence of a retro-aza Diels Alder reaction. Finally, the conformation equilibria for two new 2,4,6-triphenyl- pyridinium salts was investigated. Results were correlated with previous ones referring to analogous 2,4,6-trimethyl- salts.

Quando o tetrafluoroborato de N-(α-carbometoximetil)-2,4,6-trifenilpiridínio (Ia) foi tratado com hidróxido de potássio em etanol, resultou uma betaína que, ao ser aquecida na presença de benzaldeído ou p-clorobenzaldeído, não produziu a esperada oxazolidina IIa. Em lugar desta 1,2-di-hidropiridina, formou-se um sal cujo cátion correspondia à estrutura de um N-metil-2,4,6-trifenilpiridínio (III). Este composto resultaria da protonação da ilida intermediária, formada pela descarboxilação da betaína. Porém, quando o mesmo tipo de reação foi efetuada com o derivado α-metilado Ib, o espectro de RMN de H do produto bruto indicou a formação da di-hidropiridina (IIb), na forma de 4 estereoisômeros. A oxazolidina IIa, como um isômero largamente majoritário, pôde ser obtida pela reação do tetrafluoroborato de N-metil-2,4,6-trifenilpiridínio (III) com p-clorobenzaldeído, na presença de uma solução diluída de álcali. Esta oxazolidina era bastante instável e não pode ser purificada, sendo submetida na forma bruta à reação de Diels-Alder com a N-metil-maleimida. Esta reação conduziu a dois adutos isoméricos (IV e V). Embora o aduto majoritário (V) fosse estável em solução de deutero-clorofórmio, o aduto minoritário (IV), na presença desse solvente e à temperatura ambiente, isomerizava-se após algumas horas. A estrutura dos três adutos foi determinada por experimentos de RMN de H (NOESY e NOE 1D seletivo). A adição de um pequeno volume de solução diluída de ácido clorídrico aos compostos IV e V, dissolvidos em acetonitrila e à temperatura ambiente, resultou na isomerização catalítica desses adutos. Porém, quando esta reação de protonação foi efetuada sob refluxo de acetonitrila, formaram-se dois produtos (VI e VII), cuja estrutura era compatível com ocorrência de uma reação de retro-aza Diels-Alder. Finalmente, foi estudado o equilíbrio conformacional de dois novos sais de 2,4,6-trifenil- piridínio, e os resultados foram comparados com aqueles obtidos para os sais análogos 2,4,6-trimetil-substituídos. / When the tetrafluoroborate of N-(α-carbomethoxymethyl)-2,4,6-triphenylpridinium (Ia) was submitted to alkaline hydrolysis followed by decarboxylation upon heating, the resulting betaine failed to undergo the aldol addition reaction with aromatic aldehydes leading, in lieu of the expected oxazolidine (IIa),a salt bearing the cation N-methyl-2,4,6-triphenylpyridinium (III), as a result of the easy protonation of the intermediate ylide. However, for the corresponding a-methylated salt (Ib), the formation of four stereoisomeric 1,2- dihydropiridines was confirmed by inspection of the H NMR of the crude product. As an alternative to this method for obtaining IIa, a mixture of III and p-chlorobenzaldehyde was stirred at room temperature for several hours, in the presence of a diluted aqueous alkali. The resulting 1,2-dihidropyridine (IIa) was rather unstable precluding its isolation from the crude product mixture, and was submitted, without further purification, to the Diels-Alder reaction with Nmethylmaleimide, leading to two diastereomeric isoquinuclidines (IV) and (V). Although the major isomer showed to be stable in a deuterochloroform solution, the minor isomer (IV) underwent a spontaneous isomerization, upon standing in such solvent at room temperature. The stereochemical features of these three aducts could be accessed by NOESY and 1D NOE selective H NMR experiments. By treating a solution of adducts IV and V in acetonitrile with a small volume of aqueous HCl, at room temperature, an acid catalyzed isomerization took place. However, when the protonation reaction of the major diastereoisomer (V) was performed in acetonitrile at the reflux temperature, two products (VI and VII) were isolated, highlighting the occurrence of a retro-aza Diels Alder reaction. Finally, the conformation equilibria for two new 2,4,6-triphenyl- pyridinium salts was investigated. Results were correlated with previous ones referring to analogous 2,4,6-trimethyl- salts.

Ce travail de thèse porte sur la synthèse et la caractérisation d’élastomères réticulés réversiblement à base de polyisoprène et polybutadiène en vue de leur possible recyclage. Pour se faire, de longues chaines de polydiènes 1,4-cis ont été dégradées de manière contrôlée afin d’obtenir des polymères à faible viscosité. Dans un second temps, ces polydiènes ont ensuite été modifiés chimiquement soit le long ou soit aux extrémités des chaines afin d’obtenir des fonctions réactives de type alcool. Ces fonctions hydroxyles ont ensuite servi de point d’ancrage pour le greffage de fonctions furanes. L’addition d’un composé de type bis-maléimide au polymère liquide a alors conduit à la formation d’élastomère réticulé thermo-réversiblement grâce à la réaction de Diels-Alder entre les groupements furanes et maléimides. Les matériaux ainsi obtenus se comportement comme un élastomère réticulé stable dans une large gamme de température (- 80 °C à + 130 °C). Les propriétés mécaniques de ces élastomères (module de Young, contrainte/élongation à la rupture, module caoutchoutique) peuvent être facilement modulées en modifiant plusieurs paramètres comme la longueur des chaines, la densité de réticulation ou le lieu de réticulation (bout des chaines ou le long des chaines. La recyclabilité des matériaux a ensuite été montrée, aucune perte de propriétés n’a été observée même après 5 cycles de recyclage. Enfin, en changeant le type de liens réversibles par des groupements ureidopyrimidinones (UPy), nous avons observé que le matériel réticulé réversiblement par liaisons hydrogène obtenu possédait une organisation supramoléculaire particulière, induite par l’assemblage des groupements UPy. / This work focuses on the synthesis and characterization of reversibly crosslinked polyisoprene and polybutadiene and their potential recyclability. To this end, long chains of 1,4-cis polydienes have been degraded in a controlled manner in order to obtain telechelic polymers with low viscosity. In a second step, these low molar mass polydienes were chemically modified either along the backbone or at the chain-end of the polymer in order to obtain reactive functions. The thus obtained hydroxyl functions have been used as an anchor point for the grafting of furan functions. The addition of a bis-maleimide compound to the liquid polymer led to the formation of thermo-reversibly crosslinked elastomer thanks to the Diels-Alder reaction between the furan and the maleimide groups. The obtained materials have the behavior of a crosslinked elastomer, stable in a wide temperature range (-80 °C to + 130 °C). The mechanical properties of these elastomers (Young's modulus, strain / elongation at break, rubber modulus) can be easily modulated by modifying several parameters such as chain length, crosslinking density or crosslinking site along the chains. The recyclability of the materials was shown as no properties loss was observed even after 5 cycles of recycling. Finally, by changing the furan groups by ureidopyrimidinone groups (UPy), the reversibly crosslinked material obtained through hydrogen bonds possessed a totally different behavior with a particular supramolecular organization, induced by the assembly of the UPy groups.

The compound 2,6-anthracenedicarboxylic acid is used as a comonomer for the synthesis of poly(ethylene terephthalate). The resulting copolymers are characterized and further functionalized by Diels-Alder grafting or crosslinking through the anthracenate unit. Diels-Alder reaction is used to graft small molecules and oligomers endcapped with maleimide as dienophiles on to poly(ethylene terephthalate-co-2,6-anthracenedicarboxylate),PET-co-A. Maleimide-capped poly(ethylene glycol) is grafted onto PET-co-A to improved its hydrophilicity. 2,6-Anthracenedicarboxylic acid is also incorporated into the known liquid crystalline polymer, LCP, poly(4-oxybenzoate-co-1,4-phenylene isophthalate), HIQ40. The resulting copolymer, poly(4-oxybenzoate-co-1,4-phenylene isophthalate-co-2,6-phenylene anthracenate), HIQ40-co-A, shows LCP behavior. These HIQ40-co-A copolymers are grafted with maleimide end-capped monomers and polymers andcrosslinked with bismaleimides through a Diels-Alder mechanism.

O objetivo deste trabalho foi iniciar o estudo de uma nova metodologia sintética para a obtenção do sistema 11-oxabiciclo[6.2.1]undecano, o esqueleto estrutural básico de uma classe de produtos naturais conhecidos como furanoeliangolidos. A abordagem sintética proposta envolveria a formação de um composto bicíclico através da reação de Diels-Alder com derivados de furano, seguida pela formação de um hexanel e, finalmente, ruptura de uma ligação central para formação do sistema macrocíclico. Além disso, a reação de Diels-Alder entre derivados de furano e acetileno dará origem a compostos que apresentam como esqueleto estrutural o sistema 7-oxabiciclo[2.2.1]heptano, que podem ser utilizados como material de partida para a síntese de diversos produtos naturais. Iniciamos este estudo com a reação de Diels-Alder entre o 3,4-dimetoxi-2-metil furano e o bromopropiolato de metila, onde foi obtido o produto 85, que após algumas modificações deu origem ao composto 92. Entretanto, após inúmeras tentativas não conseguimos transformar o composto 92 no triciclo desejado. Para evitar essas transformações que se mostraram problemáticas, resolvemos estudar a reação de Diels-Alder entre derivados de furano e benzoquinonas 2,5-dissubstituídas, que dará origem aos adutos devidamente funcionalizados para serem transformados no derivado do sistema 11-oxabiciclo [6.2.1]undecano. No entanto, após o estudo dessas reações de cicloadição, observamos que elas têm o equilíbrio fortemente deslocado no sentido dos materiais de partida. Por esse motivo, a continuidade desta metodologia sintética mostrou ser inviável. Iniciamos então, um estudo da reação de Diels-Alder entre os diverso derivados de furanos e acetilenos. Após o estudo dessas reações de Diels-Alder foi possível verificar que a maioria dos adutos derivados dos furanos é instável no meio reacional. Os melhores resultados obtidos nessas reações de Diels-Alder foram usando o acetilenodicarboxilato de dimetila como dienófilo. Os adutos obtidos são intermediários importantes e bem funcionalizados, que podem ser utilizados na continuidade do estudo de desenvolvimento de nova metodologia sintética para a obtenção do sistema 11-oxabiciclo[6.2.1]undecano / The aim of this work was to start the study of a new methodology to synthesize the 11-oxabicycle[6.2.1]undecane system, the main carbon skeleton of the furanoheliangolides. The proposed synthetic approach involves the preparation of a bicyclic compound through a Diels-Alder reaction with furan derivatives, followed by formation of a six membered ring and, finally, cleavage of the central bond to obtain of the macrocyclic system. The Diels-Alder reaction between furan and acetylene derivatives gives a compound with the 7-oxabicyclico[2.2.1]heptane system, that is a potential starting material for the synthesis of several natural products. We started this study with the Diels-Alder reaction between the 3,4-dimethoxy-2-methylfuran and methyl bromopropiolate, and obtained the product 85 that after some modifications furnished the compound 92. However, after various attempts we were unable to convert the compound 92 into the desired tricycle. We have then decided to study the Diels-Alder reaction between furan and 2,5-disubstituted benzoquinone derivatives, that could furnish the adducts properly functionalized to be transformed in the 11-oxabicyclico[6.2.1]undecane system. However, we observed that the equilibrium is strongly shifted towards the starting materials in these cycloaddition reactions. This methodology has thus showed to be impracticable. As a third alternative, we affected the study the Diels-Alder reaction between the furans derivatives and the acetylenes. The adducts obtained present 7-oxabicyclico[2.2.1]heptane system that could be used to synthesizes of structural skeleton of furanoheliangolide.

Devido à sua intensa absorção de luz na região visível do espectro, as porfirinas e seus derivados (clorinas e bacterioclorinas) são de grande importância na terapia fotodinâmica (TFD) para o tratamento de doenças neoplásicas. Neste trabalho foram sintetizadas as novas vinil-porfirinas estrategicamente funcionalizadas (47 e 48), seguida de uma sistemática de reações de Diels-Alder com dieófilos ativados, com o propósito de obter clorinas e/ou bacterioclorinas para potenciais aplicações em TFD. / Due to their strong absorption in the visible region, porphyrins and related derivatives (chlorins and bacteriochlorins) are very important in photodynamic therapy (PDT) for the treatment of neoplasic diseases. In this work were synthesized the novel and strategically functionalizated vinyl-porphyrins 47 and 48, followed by systematic Diels-Alder reactions with activated dienophiles to obtain chlorins and/or bacteriochlorins, potentially useful on PDT.

The structures of Diels-Alder cycloaddition of cyclopentadiene to 2,6-dimethyl-p-benzoquinone and methylcyclopentadiene to 2,6-dimethyl-p-benzoquinone were assigned by analysis of 1-D and 2-D proton and carbon-13 NMR spectra. The structures of the cycloadduct of methylcyclopentadiene to 2,6-dimethyl-p-benzoquinone and that of the corresponding intramolecular [2+2] photocyclization product were also obtained by single crystal X-ray structural analysis. As the second part of the study, a new polycyclic "cage" molecule, a substituted trishomocubane isomer, was synthesized. In this synthesis, reductive bond cleavage followed by Dieckmann condensation was employed. Wolff-Kishner reduction then was used to convert a β-keto ester "cage" molecule to the corresponding carboxylic acid. A compound that possesses twofold symmetry was isolated from reaction product mixture. The structure of this compound has been established by single crystal X-ray crystallography.

Les benzofuroxanes sont des hétérocycles possédant des propriétés biologiques importantes. Ce type de composés possède une forte électrophilie en fonction du nombre de groupements électroattracteurs présent sur leur carbocycle. Les travaux de recherche de cette thèse s’inscrivent dans la continuité des travaux reportés dans ce domaine. Ainsi, dans une première partie purement bibliographique, sera développé l’historique de la synthèse et de la réactivité des benzofuroxanes ainsi que les travaux du laboratoire.Dans une seconde partie est présenté le développement de voies de synthèses originales vers des fluoronitrobenzofuroxanes à partir de composés simples et variés de type phénols, anisoles, et anilines. La synthèse de composés benzofuroxanes polyfluorés est ensuite présentée, revisitant la formation du 4,6-difluorobenzofuroxane qui a permis de mettre en évidence des résultats erronés de la littérature et de proposer une nouvelle méthode efficace pour sa formation. L’utilisation de la RMN à température variable a permis de déterminer sans ambiguïtés la structure de ces benzofuroxanes fluorés.Dans une troisième partie, leur réactivité est étudiée selon plusieurs méthodes, de la réactivité péricyclique à des calculs théoriques d’électrophilie globale en passant par des potentiels de réduction mesurés par voie électrochimique. Ces résultats sont comparés à d’autres électrophiles comme le trinitrobenzène en série aromatique ou le DNBF, pour les molécules superélectrophiles. De plus, la formation de quinoxalines possédant potentiellement des activités biologiques sera décrite.Dans une quatrième partie, la synthèse de composés de type benzodifuroxanes est développée. Après une introduction sur leurs caractéristiques structurales, la synthèse du 4-fluorobenzodifuroxane est décrite ainsi que la formation des analogues bromé et iodé. D’autre part la synthèse du 4-méthoxybenzodifuroxane et du 4-aminobenzodifuroxane sera décrite permettant d’apporter des informations sur la réactivité de ce type de composés.Enfin dans un dernier chapitre, la réactivité d’un électrophile chargé tel que le tropylium vis-à-vis de nucléophiles faibles indoliques sera présentée. La réaction de couplage avec le tropylium permettra de mettre en valeur la régiosélectivité de ce couplage. Les tropylidènes obtenus seront caractérisés afin de mettre en avant les caractéristiques spectrales de ce type d’adduit. Les tropylidènes formés sont ensuite oxydés afin de conduire à des tropyliums fonctionnalisés très colorés qui peuvent être aussi obtenus en une seule étape.Finalement, cette thèse s’achèvera sur une conclusion générale qui présentera aussi les perspectives sur le sujet et ce que ces travaux ont apporté à la chimie des benzofuroxanes. / Benzofuroxans are heterocycles exhibiting many biological activities. This kind of compounds has been shown to be very electrophilic spieces when substituted by electron-withdrawing groups. This work is an important part of the works reported in this field of heterocyclic chemistry. In the first part of this PhD thesis, one will find the bibliographic part dedicated to benzofuroxans including the works of our team.In a second part, the development of original synthetic pathways leading to fluoronitrobenzofuroxans from simple compounds like phenols, anisoles or anilines is shown. The synthesis of polyfluorinated benzofuroxans will be presented by revisiting the formation of 4,6-difluorobenzofuroxan highlighting erroneous published results and allowing the finding of new and efficient methods leading to the difluorinated benzofuroxan. The use of variable temperature NMR experiments allows the unambiguous determination of the structure of fluorinated benzofuroxans.In a third part the reactivity of benzofuroxans is studied using different methods such as the experimental study of the pericyclic Diels-Alder reaction, theoretical calculations of global electrophilcity and the electrochemical measurements of reduction potentials. These results are compared to those of other electrophiles like trinitrobenzene in the usual aromatic series and of 4,6-dinitrobenzofuroxan in the superelectrophilic dimension. Then, the formation of quinoxalines exhibiting potential biological activities will be described.In a fourth part the synthesis of benzodifuroxan-type compounds is developed. After an introduction dealing with their main structural features, the synthesis of the 4-fluorobenzodifuroxan and the formation of brominated and iodinated analogs are described. Then the synthesis of the 4-methoxybenzodifuroxan and the 4-aminobenzodifuroxan will bring interesting informations on the reactivity of this kind of compounds.In a last chapter the reactivity of the tropylium cation with weak nucleophiles such as indoles will be presented. The C-C coupling reactions with the tropylium cation allow the isolation of many tropylidenes moieties, which will be subsequently oxidized to lead to highly functionalized and colored substituted tropyliums.Finally, a general conclusion will summarize the significant results and the perspectives of this work in the field of benzofuroxans chemistry

Cette thèse présente la réactivité de diènes polyfonctionnalisés incorporant un atome de bore (diènes borylés) en présence de composés de type nitroso. La première partie est une étude de la réactivité des diènes borylés en présence de dérivés arylnitroso. Le produit formé ainsi que l'efficacité de la réaction est dépendant de la substitution sur l'atome de bore ainsi que du solvant utilisé pour la réaction. Suivant les conditions employées, la formation de composés avec différentes structures; pyrroles, oxazines substitués par un atome de bore, ou nitrones a été obtenue. Une stratégie one-pot a ensuite été développée pour la synthèse d'oxazolines utilisant la formation des nitrones en tant qu'intermédiaire. Des investigations théoriques et pratiques concernant le mécanisme de la formation du pyrrole ont été réalisées. La séquence expliquant la synthèse de cette structure est basée sur la cascade suivante; cycloaddition régiosélective (Nitroso Diels-Alder)/réarrangement/élimination du borate. La formation des composés de type nitrone n'a pas été totalement explicité. Des recherches sont actuellement en cours dans le but d'obtenir plus de détails sur le mécanisme mis en jeu. La deuxième partie de l'étude est orientée sur la réactivité des diènes borylés en présence de dérivés carbonylnitroso. Au contraire des dérivés arylnitroso, la nature du composé carbonylnitroso joue un rôle majeur sur la réactivité. Si le même type de réactivité engendrant la formation de pyrroles et d'oxazines substitués par un atome de bore a été observé dans certains cas, l'utilisation d'un composé carbonylnitroso étant assez pauvre en électrons génère la formation du produit issu d'une réaction nitroso-ène. Ce produit, issu de la réaction nitrosoène, a été utilisé comme intermédiaire clé pour la synthèse de différents produits polycycliques. Une séquence one-pot, multicomposants, Diels-Alder/allylboration a été optimisée donnant différentes structures suivant le dienophile et l'aldehyde employé. Dans le but de diversifier la chimie du produit résultant de la réaction nitroso-ène, une autre séquence a été mise au point utilisant la synthèse des pyrroles. Une voie multi-étape a permis la synthèse de nouvelles structures bicycliques incorporant une oxazine et un pyrrole. / This thesis presents the reactivity of dienylboronated compounds towards arylnitroso and carbonylnitroso derivatives and its use in the synthesis of heterocyclic and polycyclics compounds. The first study focused on the reactivity of dienylboronate compounds with arylnitroso derivatives resulting in pyrrole or furan products. The outcome and efficiency of the reaction is related to the boron on the dienyl moiety and the solvent used. Using the certain conditions, pyrroles, boronated MIDA ester oxazines or nitrones could be obtained. A one-pot strategy was then applied to synthesise oxazoline derivatives using nitrones as an intermediate. Theoretical, as well as experimental, work has supported that the formation of the pyrrole was obtained by a regioselective nitroso Diels-Alder reaction/rearrangement/borate elimination cascade process. Details on the nitrone formation have not been clarified, but further investigations are on-going. Secondly, attention was focused on the reactivity of dienylboronate compounds with carbonylnitroso derivatives. Contrary to the arylnitroso species, the nature of the carbonylnitroso had a dramatic impact on reactivity. On the one hand, similar reactivity towards the formation of pyrroles and boronated MIDA ester oxazines was observed, however, by employing a higher electron-deficient carbonylnitroso species, the product resulting from a nitroso-ene reaction was obtained. Ene-product was used as the key intermediate for the synthesis of different polycyclic compounds. A multicomponent, one-pot, Diels-Alder/allylboration procedure was optimised to yield various structures depending on the nature of the dienophile and the aldehyde. To diversify the chemistry of the ene-product another sequence was designed using the pyrrole synthesis. A multi-step pathway was optimised to afford novel fused bicylic oxazine-pyrrole products.

Les réactions de Diels-Alder (DA) sont connues pour leur thermo-réversibilité. A basse température, le diène et les fonctions réactives diénophiles réagissent ensemble par la réaction de (DA) pour donner l’adduit. Le but de notre thèse est d’élaborer des réseaux réticulés thermoréversibles à base époxy-amine en utilisant des réactions de Diels-Alder. La thèse est composée de cinq chapitres dont le premier est consacré à la partie bibliographique. Celle-ci résume une partie des travaux réalisés sur la synthèse d'adduits et expose les différentes conditions utilisées pour aboutir à la synthèse, ainsi que les différentes méthodes d’analyse pour la caractérisation de ces adduits. Le deuxième chapitre est consacré à la synthèse et caractérisations des pré-polymères multi-diéne furanne ester. La synthèse de ces pré-polymères a été réalisée et confirmée par la RMN-1H, avec l’apparition de nouveaux signaux entre 4 et 5 ppm prouvant l’estérification. L’analyse IR- TF confirme l’apparition des deux bandes de vibration correspondantes à la fonction ester. Le troisième chapitre est consacré à la synthèse et caractérisations des pré-polymères acides multi-diénophiles (diénophiles ouverts) et une tri-maléimide diénophile (diénophile fermé). Les analyses RMN-1H et IR-TF confirment, respectivement, la disparition des protons de la fonction amine et les deux bandes anhydride, avec ouverture de la fonction époxy. Le quatrième chapitre est consacré à la synthèse et caractérisations de pré-polymères multi-diène furane. Ceux-ci ont été réalisés par la réaction de copolymérisation entre les fonctions époxydes de la DGEBA et la phényl diglycidyl éther (PGE) avec la furfurylamine (FAM). La RMN-1H a permis de calculer la fonctionnalité en fonction furane des diènes et de déterminer leur masse molaire moyenne en nombre. L’analyse thermogravimétrie (ATG) et l’analyse thermique par DSC ont montré que ces diènes sont des composés amorphes présentant une Tg de l’ordre de 20°C et restent stables thermiquement jusqu'à une température de 230°C. Enfin, dans le cinquième et dernier chapitre, la synthèse de réseaux thermoréversibles formés par la réaction de Diels-Alder entre les pré-polymères diène et la tri-maléimide diénophile sera présentée. La thermoréversibilité, les propriétés thermiques et d’autoréparation des réseaux seront étudiées / The Diels-Alder (DA) reactions are known for their thermo-reversibility. At low temperatures, the diene and dienophile reactive functional groups react together by the reaction of (DA) to give the adduct. The aim of this thesis is to develop the thermo crosslinked networks based epoxy-amine using Diels-Alder reaction. The thesis consists of five chapters; the first is devoted to the bibliographic part. It summarizes some of the work on the synthesis of adducts and describes various conditions used to achieve the synthesis, and the different methods of analysis for the characterization of these adducts. The second chapter is devoted to the synthesis and characterization of multi-diene pre-polymers furan ester. The synthesis of these pre-polymers was carried out and confirmed by 1H-NMR, with the appearance of new signals between 4 and 5 ppm proving the esterification. FT-IR analysis confirmed the appearance of two bands corresponding to the ester vibration bands. The third chapter is devoted to the synthesis and characterization of pre-polymers multi-dienophiles acids (open dienophiles) and a tri-maleimide dienophile (dienophile closed). 1H-NMR analysis and FT-IR confirm respectively, the disappearance of the amine protons and two anhydride bands, with opening of the epoxy function. The fourth chapter is devoted to the synthesis and characterization of pre-polymers multi-furan diene. These were synthesized by the copolymerization reaction between the epoxy functions of DGEBA and diglycidyl phenyl ether (PGE) with furfurylamine (FAM). 1H-NMR was used to calculate the functionality dienes and to determine their number-average molar mass. The thermo gravimetric analysis (TGA) and the thermal analysis by DSC showed that these dienes are amorphous compounds having a Tg about 20°C and are thermally stable up to a temperature of 230°C. In the fifth and final chapter, the synthesis of thermo-reversible networks formed by the Diels-Alder reaction between pre-polymers diene and tri-maleimide dienophile will be presented. The thermoreversibility, thermal properties and self-healing networks are studied