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Réactions De Cyclisation En Cascade : Un Nouvel Accès À Des Structures Polycycliques Exotiques [4.6.4.6]Fenestradiènes Versus Cyclooctatriènes

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Réactions De Cyclisation En Cascade : Un Nouvel Accès À Des Structures Polycycliques Exotiques [4.6.4.6]Fenestradiènes Versus Cyclooctatriènes THÈSE présentée pour obtenir le grade de DOCTEUR DE L’UNIVERSITÉ LOUIS PASTEUR STRASBOURG I Discipline : Chimie Organique par Catherine HULOT Réactions de cyclisation en cascade : un nouvel accès à des structures polycycliques exotiques [4.6.4.6]fenestradiènes versus cyclooctatriènes Soutenue publiquement le 5 décembre 2008 devant la commission d’examen : Pr. Janick ARDISSON (Université Paris Descartes) Rapporteur externe Pr. Françoise COLOBERT (ECPM Strasbourg) Rapporteur interne Pr. Armin de MEIJERE (Georg-August-Universität Göttingen) Rapporteur externe Pr. Max MALACRIA (Université Paris VI) Examinateur externe Dr. Gaëlle BLOND (Université Strasbourg I) Membre invité Dr. Jean SUFFERT (Université Strasbourg I) Directeur de thèse Laboratoire de Pharmacochimie de la Communication Cellulaire (UMR 7175, LC1) THÈSE présentée pour obtenir le grade de DOCTEUR DE L’UNIVERSITÉ LOUIS PASTEUR STRASBOURG I Discipline : Chimie Organique par Catherine HULOT Réactions de cyclisation en cascade : un nouvel accès à des structures polycycliques exotiques [4.6.4.6]fenestradiènes versus cyclooctatriènes Soutenue publiquement le 5 décembre 2008 devant la commission d’examen : Pr. Janick ARDISSON (Université Paris Descartes) Rapporteur externe Pr. Françoise COLOBERT (ECPM Strasbourg) Rapporteur interne Pr. Armin de MEIJERE (Georg-August-Universität Göttingen) Rapporteur externe Pr. Max MALACRIA (Université Paris VI) Examinateur externe Dr. Gaëlle BLOND (Université Strasbourg I) Membre invité Dr. Jean SUFFERT (Université Strasbourg I) Directeur de thèse Laboratoire de Pharmacochimie de la Communication Cellulaire (UMR 7175, LC1) À Guillaume, À mes parents, À mon frère, À ma sœur. Remerciements Remerciements Je tiens tout d’abord à remercier le Dr Jean Suffert de m’avoir accueillie dans son laboratoire pour ces trois années de thèse, et de m’avoir guidée tout au long de ce travail. Je le remercie de m’avoir confié un sujet aussi passionnant et captivant. Je le remercie également d’avoir été disponible pour la moindre question, et de m’avoir fait partager toutes ses connaissances et son expérience, toujours avec le sourire et un mot d’humour. Je ne remercierai jamais assez le Dr Gaëlle Blond pour son soutien et sa confiance sans faille. En plus de ses précieux conseils du point de vue scientifique, qui ont permis de faire avancer ma thèse à grand pas, elle a toujours gardé sa bonne humeur, son dynamisme impressionnant et son enthousiasme communicatif. Que de fous rires ! Elle m’a appris à être efficace au quotidien. Un très très grand merci également pour son extrême disponibilité. Parmi les excellents souvenirs, un moment reste ainsi gravé dans ma mémoire : notre dernière répétition avant ma première communication orale à Palaiseau sur mes travaux de thèse. Je tiens à remercier chacun des membres du jury, les Prs Janick Ardisson (Université Paris Descartes), Françoise Colobert (ECPM Strasbourg), Armin de Meijere (Université Georg-August Göttingen) et Max Malacria (Université Paris VI), de me faire bénéficier de leur expertise en acceptant de juger ce travail et de consacrer du temps à l’examen de ce manuscrit. Je remercie également le Pr Peter Schreiner et Shadi Amiri (Université Justus-Liebig Giessen), pour leur collaboration fructueuse et très enrichissante concernant la partie théorique de ce manuscrit. Je les remercie de m’avoir permis de passer quelques jours très sympathiques dans leur équipe. J’aimerais ensuite remercier les anciens du laboratoire, tout d’abord les Drs Bahaâ Salem et Christophe Bour pour avoir initié ces travaux de recherche. J’en profite pour remercier également Christophe pour son aide et les bons moments durant ma première année de thèse. J’ai également eu le plaisir de travailler aux côtés du Dr Carmen Maiereanu, lors de ma deuxième année de thèse. Je tiens à la remercier vivement pour ses conseils et astuces scientifiques, tels que l’utilisation des colonnes de chromatographie, pour tous les moments très sympathiques et pour nos goûts musicaux communs. J’ai beaucoup apprécié sa chimie roumaine, avec le « brout » de réaction ! Je remercie également Régis, alias Réglisse, pour toutes nos discussions et tous nos nombreux délires durant ces années de thèse. Que ces quelques lignes leur expriment toute mon amitié. Merci également à Dimitry, Loïc, Paco, Enrique pour l’ambiance sympathique du laboratoire… Je remercie également les étudiants actuels du laboratoire, tout d’abord Aïcha, pour sa sympathie et ses nombreux cours d’allemand, quel dommage que nous n’ayons pas travaillé ensemble plus longtemps ! Merci également à Sophie, Mathieu, Thomas et en particulier Etienne qui a toujours trouvé le temps pour m’aider du point de vue informatique, de même que le Dr Nicolas Girard. Je tiens également à remercier les permanents du laboratoire, Angèle pour les discussions sympathiques et son aide, et le Dr André Mann pour sa disponibilité et ses conseils scientifiques. Remerciements Merci à Cyril, Pascale, Patrick et au Dr Bruno Didier, ainsi que toutes les autres personnes qui m’ont apporté une aide technique tout au long de ces années. Merci aux Drs Jean Peluso et Christian Muller pour leur contribution au niveau de la biologie. Merci également à Françoise et Marianne pour leur aide du point de vue administratif. Merci à tous les membres de l’UMR 7175 et de la faculté de pharmacie, en particulier à Pascal, Alexandre, Pascaline, Arthur, Ricardo, Phanélie et Clément, ainsi qu’aux personnes du laboratoire du Dr Wagner, notamment à Cynthia pour sa sympathie et pour la semaine passée ensemble à la SECO. Un grand merci au Dr Alexandre Specht pour ses conseils scientifiques et son aide, au Dr Karine Alarcon pour nos discussions, ainsi qu’aux autres membres du laboratoire du Pr Goeldner, en particulier Portia. Merci également au Dr Jean-Marc Weibel pour sa sympathie, et pour l’éthanolamine ! Je tiens à remercier aussi les Drs Viviane Van Dorsselaer et Franz Lorgé, ainsi que Véronique Rougean pour les moments forts sympathiques et très enrichissants passés à Sanofi-Aventis durant mon stage de maîtrise. Ce stage a été décisif dans mon envie de continuer dans la recherche. Merci à Franz pour la rigueur et l’organisation qu’il m’a inculquées. Merci également aux amis : Maher alias Mac, mon meilleur ami, ancien trinôme de chimie du DEUG, qui m’a montré notamment comment on pouvait s’amuser en chimie, ainsi que sa petite famille Tatiana et Yannis ; Carole alias ma folle, mon amie depuis notre rencontre mémorable lors du premier jour du DEUG ; le Dr Aurélie Guenet et Mathieu l’autre fan du PSG bien malheureux ! pour nos supers soirées animées ; le Dr Ludivine Fetzer, pour son écoute et nos discussions de thésardes ; Cécile alias Cess, que de chemin parcouru depuis le CP ! et Fabrice ; Caro, pour tous nos délires ; Marion et Hervé alias Pinpon Pro, qu’ils reçoivent toute mon estime ; le Dr Djalil Coowar et le Dr Mazen Hanbali, pour leur aide lors de mon DEA. Pour finir, un petit clin d’œil à mon petit chat Molybdène ! Je souhaite remercier profondément mon père, ma mère, mon frère et sa copine Marine, et bien entendu ma soeurette, pour m’avoir soutenue et comprise tout au long de ce travail. Sans eux, rien de tout cela n’aurait été possible ! Je pense que le fait de cotoyer des spectromètres RMN Bruker dès mon plus jeune âge avec mon père m’a probablement poussée dans cette direction ! Ils m’ont encouragé tout au long de ma scolarité. Que cette thèse leur soit dédiée. Merci aussi à mes grands- parents, qui ont toujours eu confiance en moi, ainsi qu’à toute ma famille. Je ne pourrais pas terminer sans remercier du fond du cœur Guillaume, pour son amour et sa présence dès la première année de DEUG. Merci tout simplement d’être à mes côtés. Je suis heureuse qu’on puisse vivre l’aventure de nos deux thèses ensemble, chacun dans son domaine. Un grand merci également pour son aide informatique durant cette rédaction, sans lui, le manuscrit ne serait pas ce qu’il est actuellement. Je ne compte plus les heures qu’il a passées à m’aider ! Que cette thèse lui soit dédiée. Je tiens également à remercier son père pour son soutien indéfectible, son frère, et je pense très fort à sa mère qui a toujours cru en nous et qui, je l’espère, est fière de nous de là-haut. Abréviations et symboles Abréviations et symboles Å angström FDA food and drug administration Ac acétyle FT-IR infrarouge à transformée de Fourier AcOEt acétate d’éthyle g gramme AIBN 2,2-azobisisobutyronitrile g.mol-1 gramme par mole Ar aryle h heure arom aromatique hfacac hexafluoroacétylacétonate AsPh3 triphénylarsine HMBC heteronuclear multiple bond BER borohydride exchange resine correlation BHT 3,5-di-tert-butyl-4-hydroxytoluène HMPA hexaméthylphosphoramide Bn benzyle HOMO highest occupied molecular orbital Boc tert-butyloxycarbonyle HRMS high resolution mass spectra BSA N,O-bis(triméthylsilyl)acétamide HSQC heteronuclear single quantum i-Bu iso-butyle coherence n-Bu n-butyle Hünig N,N-diisopropyléthylamine t-Bu tert-butyle Hz hertz n-BuLi n-butyllithium Im imidazole n-Bu3N n-tributylamine IR infrarouge n-BuNH2 n-butylamine j jour t-BuOH tert-butanol Ki constante d’inhibition t-BuOK tert-butanolate de potassium LDA diisopropylamidure de lithium cat. quantité catalytique LHMDS hexaméthyldisilazidure de lithium CCM chromatographie sur couche mince LUMO lowest unoccupied molecular orbital CDCl3 chloroforme deutéré lutidine 2,6-diméthylpyridine CHBr3 bromoforme m multiplet -1 CH2Cl2 dichlorométhane M mol.L CHCl3 chloroforme Me méthyle CH3CN acétonitrile Men menthyle cm centimètre MeOH méthanol
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