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Co-Crystallization Induced Spontaneous Deracemization

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I UNIVERSITÉ CATHOLIQUE DE LOUVAIN INSTITUTE OF CONDENSED MATTER AND NANOSCIENCES (IMCN) Laboratory of Crystal Engineering Prof. Tom Leyssens Laboratory of Organic Chemistry Prof. Olivier Riant Development and Optimization of a new general thermodynamic deracemization method: Co-crystallization Induced Spontaneous Deracemization Thèse présentée en vue de l'obtention du grade de docteur en Sciences par Michael Guillot Louvain-la-Neuve Septembre 2020 II Jury Members Prof. Y. Cartigny Université de Rouen Normandie Prof. S. Kuhn Katholieke Universiteit Leuven Prof. M. Singleton Université catholique de Louvain Dr. K. Robeyns Université catholique de Louvain Prof. Y. Garcia (President) Université catholique de Louvain Prof. T. Leyssens (Promotor) Université catholique de Louvain Prof. O. Riant (Co-promotor) Université catholique de Louvain III Acknowledgements Je tiens tout d’abord à remercier mon promoteur, le professeur Tom Leyssens de m’avoir offert la chance de faire partie de son laboratoire pendant ces 4 années qui furent épanouissantes sur tous les plans. Je le remercie pour son encadrement tout au long de ma thèse, pour son soutien tant scientifique que personnel (surtout pendant « the dark year » où plus rien ne semblait marcher, je pense que tu vois de quel moment je parle Tom ;)) et pour la proximité qu’il sait créer au sein de son équipe. Je le remercie pour les congrès et séjours scientifiques que j’ai pu réaliser grâce à lui et qui ont tant participé à mon apprentissage autant scientifique que personnel. Je tiens tout aussi à remercier mon co-promoteur, le professeur Olivier Riant, pour ses conseils et corrections tout au long de ces quatres années de thèse. Je remercie aussi tous les membres du jury pour le temps qu’ils ont passé à évaluer cette thèse. I would also like to thank Professor Joop ter Hoost for welcoming me into his team and allowing me to carry out part of this research in his laboratory. Now, I will go on by thanking Vanessa aka Vanish aka my BFF for those almost 4 years by my side (almost because you abandon me right before the end you bitch <3). You were always there when I needed you. You helped me more than you can imagine and the end of my PhD without you was not as great as it could have been with you. Getting to know you was the best part of my PhD but not entirely… Oui Xa aka Chou aka Dr. Xavier Buol, je te mets à égalité avec Vanessa sur ce point, te rencontrer est la meilleure partie de ma thèse. Tu as été là pour moi pendant ces 4 années de doctorat qu’on a en gros réalisées ensemble. Tu as su m’épauler pendant les moments difficiles (j’espère que ton t-shirt a réussi à sécher à présent ;)) et supporter mon chant. Tu as su me calmer dans mes divagations et m’écouter quand j’en avais besoin. T’es mon bro avec ses gros bibis, ti amo <3. A présent, parlons de toi Carole aka Carolus. Tu as été ma première mémorante mais surtout une très belle rencontre au sein du laboratoire. Et je suis content que tu aies décider de revenir faire une thèse parmi nous et de pouvoir dire que tu es mon amie et ce même si tu as filmé cette fameuse vidéo à la gaypride que tu as accidentellement envoyé à Tom (oups !). Pour continuer chez les mémorantes, même si Sarah tu n’étais pas ma mémorante officielle, je te remercie quand même pour tout ce que tu as su apporter, ainsi que comme Carole pour ton aide lors de l’organisation de la STEL. Le marteau de Thor est encore à la cafétéria et j’espère qu’il y restera en souvenir de notre passage. Enfin, merci d’avoir permis à Joséphine de devenir ma deuxième mémorante officielle. Jo, je te remercie pour toute l’aide que tu m’as apporté sur la fin de ma thèse. J’ai pu compter sur toi comme personne et je suis vraiment désolé que tu aies eu à payer mes problèmes relationnels avec certaines personnes durant ton mémoire. Je sais très bien que tu avais fermé cette bouteille d’azote, je n’en ai jamais IV douté . Je suis aussi content que tu commences ta thèse au sein du groupe de Tom et te souhaite tout le succès que tu mérites. Je vais maintenant remercier Aurore aka Aurorus, la maman de l’étage, je ne pense pas t’avoir déjà appelé comme cela mais c’est ce que tu représentes pour tout l’étage je pense et ce que tu as représenté pour moi durant ces 4 années de doctorat. Au moindre problème administratif tu as su m’aider (et que Tom en soit témoin l’administratif et moi ça fait 2), dans mon rôle de président STEL comme de membre ACIM tu as aussi su m’être indispensable. Je te remercie aussi pour tout ce que tu es et la bonne humeur que tu sais transmettre au sein de l’étage. Si comme moi, certains ont voulu te mettre des bâtons dans les roues et même si tu y as perdu des plumes, tu es restée et reste l’oiseau de valeur de notre étage. Tu es une secrétaire et personne en or. On se revoit quand tu pars à la retraite <3. Pour continuer avec l’étage B1, je remercie Véro (et son côté râleur qui m’aura bien fait rire, ne change pas, râler c’est bon pour la santé !), Claire, Camila, Paolo, Martin, Kévin, Max, Nicolas, Tim, Lixing, Jean-Baptiste, Ricky, Gabriel, Fabrice, Bram, Benjamin, mon stagiaire IPL Elysée et toutes autres personnes qui ont permis à cet étage d’être aussi agréable et bonne ambiance contrairement à d’autres étages. Je vais spécialement remercier Ricky et Jean-Baptiste, aka JB, mes collègues de bureau pendant 3 ans, pour ces bons moments partagés. Et surtout merci Ricky de m’avoir défendu comme tu l’as fait alors que tu n’y étais pas du tout obligé. Ça a beaucoup compté pour moi. JB, je sais qu’on a eu nos hauts et nos bas, on n’a pas toujours été d’accord sur tout, mais tu reste une très belle rencontre. Je souhaite aussi remercier toutes les personnes qui m’ont aidées et avec qui j’ai passé de très bons moments lors de mon séjour dans le laboratoire du Professeur Ter Hoost et tout spécialement Maxime, Charline, Erin, Georgia, Russel, Jenna & Andrew. Je souhaite remercier tous ceux qui m’ont aidé à organiser ces deux STEL en tant que président (Sébastien, Michael (A)) et tous les membres ACIM que j’ai eu plaisir à rencontrer (remerciement tout spécial à Quentin). Je souhaite remercier tout spécialement Mathilde, Sébastien, Mathieu, Céline, Audric (M), Marine et Corentin (L) du groupe Riant pour leur aide et leur gentillesse. Audric (M), je suis très content d’avoir pu te rencontrer pendant ton mémoire, d’avoir appris à te connaître et d’être devenu ton ami, monsieur le MJ. Je remercie aussi Nathalie, Saroj, Kiran, Junjie et Yonghua du groupe Riant. Je tiens aussi à remercier toutes les personnes qui ont contribué non directement et pourtant tout aussi essentiellement : Mes besties Claire et Anaïs, malgré la distance rien ne change entre nous et j’espère que cela continuera ainsi jusqu’à ce que l’on soit vieux. Cora qui même si elle avait quitté le club des célib fut mon modèle tinder ;) Stéphane, mon plus vieil ami, on ne se voit pas souvent mais le peu de fois, c’est comme si le temps n’avait pas passé. Michaele, Martin, Martin Hélène, Florence et Davide, les colocs des combattants pour tous ces bons moments et ses fous rires, big V up à Mike pour ces moments de proses inoubliables et ses discours qui ne sont pas tombé dans l’oreille d’un sourd. Enfin, je remercie Ousam, Giulia, Florence et Max, les colocs de la ramée pour cette très bonne dernière année passée à leur côté. Je remercie spécialement Ousam et Giulia qui sont des personnes formidables que je suis content d’avoir pu rencontrer et devenir ami avec. Oh Djadja c’est pour toi Giu. Ousam, mon bon couillon, je te remercie de m’avoir proposé cette colocation et n’oublie pas, derrière ton côté beau parleur, tu es un mec en or. Enfin, je remercie mes parents et ma sœur qui malgré la distance ont su être là pour moi. Vous devriez revenir en Belgique, on visitera Pairi daiza ! (Une fois cette histoire de Corona passée). VI List of Publications 1. T. Leyssens, R. A. Couch, M. Guillot, B. Harmsen T. R. Bailey, M. Appelmans. Solid Forms of Fasoracetam. (2019). WO2019143824A1. 2. M. Guillot, J. de Meester, S. Huynen, L. Collard, K. Robeyns, O. Riant, T. Leyssens, Angew. Chem. Int. Ed. 2020, 132, 28, 11399- 11402. 3. M. Guillot, J. de Meester, J. H. ter Host, O. Riant, T. Leyssens, Fungicide precursor racemization kinetics for deracemization in complex systems. Eur. J. Org. Chem. 2020. VII Abstract In pharmaceutical industry, 50% of the marketed drug compounds contain a chiral center, essential to their functioning. Where one enantiomer has the desired pharmacological effect, the other might be inactive, equally active or have adverse effects. For this reason, development of enantiopure drugs is strongly recommended by regulation authorities to industries. The industrially most prominent way to enantiopure drugs still involves formation of a racemic compound, followed by a chemical or physical resolution. Such a resolution implies a maximum yield of 50%, as the unwanted enantiomer is discarded upon separation.
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    Chapter 8. Chiral Catalysts José M. Fraile, José I. García, José A. Mayoral 1. The Origin of Enantioselectivity in Catalytic Processes: the Nanoscale of Enantioselective Catalysis. Enantiomerically pure compounds are extremely important in fields such as medicine and pharmacy, nutrition, or materials with optical properties. Among the different methods to obtain enantiomerically pure compounds, asymmetric catalysis1 is probably the most interesting and challenging, in fact one single molecule of chiral catalyst can transfer its chiral information to thousands or even millions of new chiral molecules. Enantioselective reactions are the result of the competition between different possible diastereomeric reaction pathways, through diastereomeric transition states, when the prochiral substrate complexed to the chiral catalyst reacts with the corresponding reagent. The efficiency of the chirality transfer, measured as enantiomeric excess [% ee = (R−S)/(R+S) × 100], depends on electronic and steric factors in a very subtle form. A simple calculation shows that differences in energy of only 2 kcal/mol between these transition states are enough to obtain more than 90% ee, and small changes in any of the participants in the catalytic process can modify significantly this difference in energy. Those modifications may occur in the near environment of the catalytic centre, at less than 1 nm scale, but also at longer distances in the catalyst, substrate, reagent, solvent, or support in the case of immobilized catalysts. This is the reason because asymmetric