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Thesis Reference Thesis Modular synthesis and applications of chiral Tunable Dyes and Fluorophores WALLABREGUE, Antoine Abstract The goal of this PhD was to explore the reactivity of a novel N-aminoacridinium salt. This derivative has been used for the preparation of pH-sensitive and fluorescent diaza [4]helicene dyes thanks to particularly facile N-N bond cleavage reactions. This compound has also been used as nitrogen source for the stereospecific aziridination and sulfoximination of unfunctionalized olefins and sulfoxides under metal-free oxidative conditions respectively. The corresponding NH aziridines and sulfoximines were then obtained using mild photoreductive conditions. Moreover, N-aminoacridinium salt was utilized for the preparation of the fisrt small fluorophore (pKa 5.3) which specifically stains for late endosome compartments (pH 4.8-6) and for the synthesis of chiral (helical) BODIPY and azobenzene derivatives. Reference WALLABREGUE, Antoine. Modular synthesis and applications of chiral Tunable Dyes and Fluorophores. Thèse de doctorat : Univ. Genève, 2015, no. Sc. 4831 URN : urn:nbn:ch:unige-761582 DOI : 10.13097/archive-ouverte/unige:76158 Available at: http://archive-ouverte.unige.ch/unige:76158 Disclaimer: layout of this document may differ from the published version. 1 / 1 UNIVERSITÉ DE GENÈVE FACULTÉ DES SCIENCES Section de chimie et biochimie Département de chimie organique Professeur Jérôme Lacour Modular Synthesis and Applications of Chiral Tunable Dyes and Fluorophores THÈSE présentée à la Faculté des sciences de l’Université de Genève pour obtenir le grade de Docteur ès sciences, mention chimie par Antoine WALLABREGUE de Dakar (SENEGAL) Thèse N° 4831 GENÈVE Atelier d’impression ReproMail 2015 Publications: “Modular synthesis of pH-sensitive fluorescent diaza[4]helicenes” Wallabregue, A.; Sherin, P.; Guin, J.; Besnard, C.; Vauthey, E.; Lacour, J.; Eur. J. Org. Chem. 2014, 6431. “Selective imaging of late endosomes with a pH-Sensitive diazaoxatriangulene fluorescent probe” Wallabregue, A.; Moreau, D.; Sherin, P.; Vauthey, E.;Gruenberg, J.; Lacour, J.; Manuscript Submitted. “Stereospecific synthesis of unprotected aziridines and sulfoximines using acridinium ion as photoremovable group” Wallabregue, A.; Popper, M. L.; Moneva Lorente, P.; Lacour, J.; Manuscript in preparation. à ma fille Sarah, ma famille et en mémoire de mes grand parents Remerciements Remerciements Les résultats rapportés dans ce manuscrit ont été obtenus dans le cadre d’un travail de thèse réalisé au sein du laboratoire du Prof. Jérôme Lacour, dans le département de chimie organique de l’Université de Genève, du 1er Octobre 2010 au 25 Septembre 2015. J’exprime toute ma gratitude et ma reconnaissance au Prof. Jérôme Lacour pour m’avoir donné l’opportunité d’intégrer son groupe de recherche, pour ses conseils, pour la confiance et le soutien qu’il m’a toujours accordé. Je tiens aussi à remercier le Prof. Nathalie Katsonis (Université de Twente) et le Prof. Nicolas Winssinger (Université de Genève) d’avoir eu l’amabilité de bien vouloir juger ce travail de thèse. Je désire ensuite remercier les équipes du service d’analyse: RMN (André Pinto, Marion Pupier et le Dr. Damien Jeannerat), Mass (Eliane Sandmeier, Harry Theraulaz et le Dr. Sophie Michalet) et ainsi que le service de cristallographie (Dr. Laure Guénée et Céline Besnard) pour leur indispensable contributions. Un remerciement particulier à Marie-Louise Popper, Mahesh Vishe, Irene Hernandez, Cecilia Tortoreto, Pau Moneva (alias Mr Pel), au Dr. Amalia Isabel Poblador-Bahamonde, au Dr. Thierry Achard et Dr Florian Médina, pour de nombreuses raisons que je ne peux détailler ici, mais travailler avec vous, a été une expérience enrichissante et spéciale. Une mention spéciale aux Dr. Petr Sherin et Dr. Dimitri Moreau pour nos collaborations enrichissantes et fructueuses. Je tiens ensuite à remercier le Dr. Florian Medina, le Dr. Sébastien Goudedranche, le Dr. Johann Bosson et le Dr. Romain Duwald pour les corrections apportées à ce manuscrit. Il me reste à remercier mes collègues du laboratoire et du département, en particulier: Sté, p’tit Jéjé, Joël, Léo, Alvina, Irene, Alex Combi, Alex Boss, Alejandro (alias Mme Pel), Géraldine, Maya, Danièle, Sandip, Steven, Radim, David, Franck, Jérémy, Manon, David Alonso, Jezabel, Ludovic, Marta, Julio, Christophe, Xiao, Les Sonia, Mireille, pour avoir rendu chaque jour au laboratoire un peu spécial et ces cinq ans inoubliables. Enfin un grand merci à ma famille à qui je dois tout et sans qui rien de tout ça n’aurait été possible. Tout d’abord mes parents, vos sacrifices quotidiens et les valeurs que vous m’avez transmis m’ont quotidiennement inspirés et permis d’en être à ce stade aujourd’hui. Je ne puis vous témoigner toute ma gratitude et ma reconnaissance tellement elles sont grandes, mais je peux vous dire une chose, je vous aime et je suis plus que fier d’être votre enfant. Merci Remerciements également à Yérim et Robert qui il y a 14 années de cela m’ont accueilli, soutenu financièrement et moralement et m’ont permis de poursuivre mes études secondaires et universitaires. Merci à Noël, Jean-Marc, Elisabeth, Pierre, Paméla, Tiffany et Thérèse ,vous êtes des frères et sœurs que tout le monde rêverait d’avoir, je demande à dieu que nous restions toujours unis et que chacun d’entre vous puisse s’épanouir et réaliser son rêve. Merci également à Fati pour ces nombreuses années à mes côtés et ton soutien, nos chemins se sont peut être séparés mais la vie nous a donné un merveilleux cadeau qui nous lie à jamais, notre princesse Sarah. A tous et toutes, merci pour votre soutien indéfectible et votre amour. Abbreviations R : Retardation factor f s: Singulet Abbreviations, symbols and units S Ar: Electrophilic aromatic substitution E S Ar: Nucleophilic aromatic substitution Abbreviations N BODIPY: Boron-dipyrromethene SM: Starting material brs: Broad singulet t: Triplet CD: Circular dichroism td: Triplet of doublets COSY: Correlation spectroscopy TD-DFT: Time-dependent density functional theory d: Doublet TLC: Thin layer chromatography DCM: Dichloromethane UV: Ultraviolet dd: Doublet of doublets Vis: Visible DFT: Density functional theory DIPEA: N,N-Diisopropylethylamine DMF: N,N-Dimethylformamide Symbols DMQA: Dimethoxyquinacridine δ: Chemical shift dt: Doublet of triplets ε: Extinction coefficient EDG: Electron donating group λ: Wavelength Equiv: Equivalent(s) Φ : Quantum yield ESI-MS: Electrospray ionization mass f υ: Wavenumbers spectrometry J: Coupling constant EWG: Electron withdrawing group τ: lifetime HMBC: Heteronuclear multiple-bond correlation spectroscopy Units HOMO: Highest occupied molecular °C: Degree(s) Celsius orbital µl: Microliter(s) HPLC: High-performance liquid g: Gram(s) chromatography h: Hour(s) HRMS: High-resolution mass Hz: Hertz spectrometry M: Molarity HSQC: Heteronuclear single-quantum mg: Milligram(s) correlation spectroscopy MHz: Megahertz IR: Infrared min: Minute(s) LUMO: Lowest unoccupied molecular orbital ml: Milliliter(s) mmol: Millimole(s) m: Multiplet MO: Molecular orbital mol: Mole(s) MS: Molecular sieves nm: Nanometer(s) NBS: N-Bromosuccinimide NCS: N-Chlorosuccinimide NIS: N-Iodosuccinimide NMP: N-Methyl-2-pyrrolidone NMR: Nuclear magnetic resonance No.: Number NOESY: Nuclear Overhauser effect spectroscopy PEG: Polyethylene glycol PET: Photoinduced electron transfer ppm: Part(s) per million Résumé Modular Synthesis and Applications of Chiral Tunable Dyes and Fluorophores Récemment une classe particulière d’hélicènes cationiques dénommés dimethoxyquinacridinium DMQA+ 1.43 a été synthétisé à partir d’un simple précurseur cationique 1.45 (Schéma 1).1 Schéma 1: Synthèse du DMQA+ 1.43. Ces dérivés, qui peuvent contenir des atomes d'oxygène et/ou d'azote substitués sont ‡ -1 2 chimiquement et configurationnellement stables (ΔGracem ≈ 42 kcal.mol à 200 °C). Cette + stabilité a été mise en évidence par des valeurs de PKR mesurées assez élevées (comprises entre 14 et 19) et a ainsi permis l’étude de ces hélicènes cationiques dans différents domaines allant de la chimie-physique à la biologie.3 En plus, ces colorants présentent des propriétés optiques dans le domaine du rouge et du proche infrarouge du spectre électromagnétique de la lumière, faisant de ce fait de ces molécules, des membres de la sous famille des hélicènes azotés fluorescents. En général, la grande stabilité des DMQA+ 1.43 les rend insensibles aux variations de pH (2 <pH <8) et par conséquent, leurs propriétés d'absorption et d'émission ne varient pas avec l'acidité du milieu dans lequel ils sont dissous. Cette insensibilité au pH environnant, a été considérée comme une limitation, et la possibilité de synthétiser des senseurs de pH chiraux a été jugé intéressante. En effet, peu de composés de ce type ont été 1 a) B. W. Laursen, F. C. Krebs, Chem. Eur. J. 2001, 7, 1773-1783; b) B. W. Laursen, F. C. Krebs, Angew. Chem. Int. Ed. 2000, 39, 3432-3434. 2 a) J. Gouin, T. Bürgi, L. Guénée, J. Lacour, Org. Lett. 2014, 16, 3800; b) J. Guin, C. Besnard, J. Lacour, Org. Lett. 2010, 12, 1748; c) C. Herse, D. Bas, F. C. Krebs, T. Bürgi, J. Weber, T. Wesolowski, B. W. Laursen, J. Lacour, Angew. Chem., Int. Ed. 2003, 42, 3162 3 a) J. Bosson, J. Gouin, J. Lacour, Chem. Soc. Rev. 2014, 43, 2824; b) F. Dumitrascu, D. G. Dumitrescu, I. Aron, ARKIVOC 2010, 1. i Résumé reporté. C’est donc logiquement, qu’il a été décidé d'introduire un atome d'azote basique à la périphérie du squelette du [4]hélicène afin de résoudre ce problème. Cela a été réalisé grâce à l’utilisation d’un nucléophile α tel que l’hydrazine, qui a été utilisé comme donneuse d’atome d’azote. C’est ainsi qu’avec l’usage de deux stratégies de synthèse complémentaires, dont la plus convergente (voie B) s’appuie sur l’utilisation de l’ion acridinium 2.5j comme précurseur central, qu’une grande variété de colorants racémiques 2.4 (11 molécules) avec divers substituants a été synthétisé en deux étapes seulement (Schéma 2). Les rendements de cette réaction varient entre 60 et 90%.4 Schéma 2: Les différentes voies de synthèse utilisées pour la préparation des colorants 2.4.
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