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New Catalysts for the Enantioselective Addition of Diorganozinc Compounds to Aldehydes and Imines

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New Catalysts for the Enantioselective Addition of Diorganozinc Compounds to Aldehydes and Imines UNIVERSITE CATHOLIQUE DE LOUVAIN FACULTE DES SCIENCES Unité de Chimie Organique et Médicinale Professeur L. GHOSEZ New Catalysts for the Enantioselective Addition of Diorganozinc Compounds to Aldehydes and Imines Dissertation présentée en vue de l'obtention du grade de Docteur en Sciences par Jérôme HOET 2005 Composition du jury : Dr. P.G. Cozzi Università degli studi di Bologna (I) Pr. A. Noels Université de Liège, Liège (B) Prof. I. Markó Université catholique de Louvain Prof. J. Marchand-Brynaert (Président) Université catholique de Louvain Prof. O. Riant (Promoteur) Université catholique de Louvain Prof. L. Ghosez (Promoteur) Université catholique de Louvain Ce travail n'aurait pas pu voir le jour sans un nombre impressionnant de personnes envers lesquelles je suis très reconnaissant. Ainsi, je tiens plus particulièrement à remercier, Monsieur le Professeur Léon Ghosez pour m'avoir accueilli au sein de son laboratoire et pour la latitude qu’il m’a accordée dans le développement de mon travail. Monsieur le Professeur Olivier Riant pour ses idées et ses conseils judicieux dans le domaine de la catalyse asymétrique. Tous les membres d'ORSY et de CHOM (ex-CHOR) qui au cours de ces nombreuses années m'ont témoigné leur amitié et ont su créer une ambiance propice au travail… et à la détente. Une mention toute particulière à Didier Schils, Laurent Trembleau, Patrick Schanen, Sébastien Lemaire et Benoît Mathieu qui ont pris le temps de me donner leur avis scientifique lors de nombreux "séminaires impromptus". Van et ses trois "poulettes", Huguette, Anny et Chantal, pour la qualité de leurs innombrables services, leur présence et leur gentillesse. Jean-Michel Adam, Patrick Schanen et Patrick Pouplard, trois générations d'informaticiens "maison", pour leur acharnement à résoudre nos crashs et autres bugs en plus de leurs soucis chimiques. Monsieur le Professeur André Schanck, Benoît Mathieu et David Chapon, pour leur aide et leur patience lors de l'enregistrement et l'interprétation des spectres RMN à haut champ. Monsieur Willy Verbist pour avoir "accordé" avec minutie les instruments de RMN de routine et ressuscité de nombreuses calottes chauffantes. Monsieur le Professeur Edmond De Hoffmann et son équipe de l'unité de spectrométrie de masse. Monsieur le Professeur Bernard Tinant qui a effectué les analyses cristallographiques. Jean-François Stassen du laboratoire du Professeur Michel Devillers pour les nombreux essais de thermogravimétrie des complexes du cuivre. Christian Coppens de l'atelier de soufflage de verre pour son travail d'orfèvre. Charles "Charly" Penneman et Edouard Vandendorpel pour l'achalandage du Magasin Lavoisier ainsi que René Bidoul pour son aide logistique dans le laboratoire. Le FRIA et l'UCL pour leur soutien financier. Les professeurs et industriels qui ont mis de précieux ligands chiraux à notre disposition. Ceux-ci sont cités à la fin de cette thèse. Tous ceux qui, avec patience et amitié, ont contribué à la réalisation finale de ce manuscrit : Bernard Leroy, Michael De Paolis, Guillaume Berthon, Nicolas Vriamont, Jérôme Hannedouche, Yann Pressel, et en particulier Catherine pour son aide précieuse 48 heures avant la mise sous presse. "Son atome" (de zinc, bien sur) tient tout spécialement à remercier l'inégalable, l'irremplaçable, l'inénarrable (…l'insupportable parfois aussi) "Chanchan" sans qui, il est vrai, le Laboratoire ne serait… qu'un laboratoire. Laurent "Tromblon" et Didier Schils, les "laids de la Rive" pour leur aide et amitié irremplaçable. Enfin, merci à vous, Catherine, Sara, Marie-Eve et Patrick qui avez vécu cette thèse presque autant que moi… Votre présence, votre soutien sans cesse renouvelé ont ainsi contribué à ce que je puisse enfin écrire…le mot "FIN". Résumé Cette dissertation traite de l'activation de composés diorganozinciques par des catalyseurs asymétriques dans le cadre de leur addition énantiosélective sur des doubles liaisons carbone-oxygène et carbone-azote. Les propriétes de divers catalyseurs originaux ont été investiguées. Plusieurs sulfonamidoalcools chiraux dérivés du (S)-leucinol et du (1S)-3-aminoisoborneol ont été synthétisés pour couvrir un domaine de propriétés électroniques et stériques. Ceux-ci ont été testés lors l'addition du Et2Zn sur les N-phosphinoyl et N-sulfonyl-imines, mais ils n'ont pas fourni de rendements et excès énantiomériques intéressants malgré leur utilisation en quantité stoechiométrique. Leurs propriétés catalytiques ont également été examinées dans le cadre de l'addition de Et2Zn au benzaldéhyde. Malheureusement, un faible contrôle de l'énantiosélectivité (max. 47% ee) est obtenu en présence de 10mol% de ligand chiral. Une autre approche abordée concerne l'influence de l'anion fluorure sur la nucléophilie des composés dialkylzincs envers le benzaldehyde. La combinaison de quantités stoechiométriques d'un sel fluoré inorganique et d'une quantités sub-stoechiométrique d'un agent de transfert de phase (10mol% éther couronne 18-C-6) conduit à un accroissement non négligeable de la vitesse de réaction. Toutefois, le développement d'une version asymétrique de ce système n'a pas été considéré. A la suite de notre découverte de l'activation due à l'anion fluorure, les complexes métalliques fluorés ont été examinés en tant que catalyseurs potentiels. En particulier, le complexe du cuivre, (Ph3P)3CuF, accélère la réaction d'addition du Et2Zn sur le benzaldéhyde. Après un criblage de divers ligands, la combinaison de (Ph3P)3CuF et de la diphosphine chirale BINAP en quantité catalytique (1mol%) conduit à une catalyse efficace de l'addition du Et2Zn sur des aldéhydes aromatiques. Les rendements obtenus sont bons, par contre l'énantiosélectivité est modeste (49-63% ee). Une version améliorée de catalyseurs cuivre-fluorure a été obtenue en combinant un sel de cuivre, une source de fluorure et une diphosphine chirale. L'optimisation de divers paramètres de réaction a été effectuée (source de cuivre, origine de l'anion fluorure, ligand chiral, stoechiométries relatives des précurseurs du catalyseur, charge de catalyseur, solvant et température). Le catalyseur optimisé a été appliqué à divers aldéhydes (jusqu'à 87% ee). Un mécanisme réactionnel a été proposé sur la base d'arguments de la littérature et d'observations expérimentales. Le rôle du contre-ion a été exploré par un examen attentif de divers complexes du cuivre en combinaison avec la BINAP chirale en tant que catalyseurs de l'addition du Et2Zn sur le benzaldehyde. Les dicétonates du cuivre(II) ont conduit à une bonne énantiosélectivité (jusqu'à 88% ee) qui a pu être améliorée en utilisant des dicétonates du cuivre(II) optiquement actifs assortis avec le bon énantiomère de la BINAP (jusqu'à 91% ee). Ce nouveau système a été appliqué pour l'addition du Et2Zn sur divers aldéhydes avec une charge réduite en catalyseur (0.5mol%). Un mécanisme a été proposé afin de supporter les observations expérimentales. Mots-clés : diorganozincique, aldéhyde, cuivre, fluorure, 1,3-dicétonate, énantiosélectivité Abstract This PhD thesis deals with the activation of diorganozinc compounds by asymmetric catalysts in the framework of their enantioselective addition on carbon-oxygen and carbon-nitrogen double bonds. The properties of several new catalysts systems were investigated. Several chiral sulfonamido alcohols derived from (S)-leucinol and (1S)-3-aminoisoborneol were synthesized to cover a range of electronic and steric properties. These were evaluated in the addition of Et2Zn to N-phosphinoyl and N-sulfonyl-imines, but they did not provide any acceptable yields or enantioselectivities while used in stoichiometric quantities. Their catalytic properties were also investigated for the addition of Et2Zn to benzaldehyde. Unfortunately, only modest enantiocontrol (max. 47% ee) could be obtained with 10mol% of chiral ligand. We investigated another approach based on the possible activation of the nucleophilicity of dialkylzinc compounds towards benzaldehyde by fluoride anion. The combination of stoichiometric amount of an inorganic fluoride salt and a substoichiometric amount of a phase transfer catalyst (10mol% of crown ether 18-C-6) provided non-negligible rate acceleration. However, an asymmetric version of this catalytic system was not considered. Following our discovery of the activation provided by the fluoride anion, metal fluoride complexes were tapped as potential catalysts. In particular, copper(I) fluoride complex, (Ph3P)3CuF, was shown to accelerate the reaction on benzaldehyde. After screening a range of ligands, the combination of (Ph3P)3CuF and chiral BINAP in catalytic amounts (1mol%) was found to catalyze efficiently the Et2Zn addition on aromatic aldehydes. Yields were good but enantiocontrol was modest (49-63% ee). An improved copper fluoride-based catalyst was developed by combining a copper salt, a fluoride source and a chiral diphosphine ligand. Optimization of this second generation catalyst was carried out (copper source, fluoride source, chiral ligand, relative stoichiometries of catalyst’s precursors, catalyst’s loading, solvent, temperature) and applied to a range of aldehydes (upto 87% ee). A mechanism was proposed based on literature data and experimental observations. The influence of the counterion was then thoroughly explored by assessing the catalytic potential of various copper complexes in combination with chiral BINAP in the Et2Zn addition to benzaldehyde. Copper(II) diketonates provided good enantiocontrol (upto 88% ee) which could be improved even further by using optically active
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