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Arene Complexes – an Odyssey Towards a Revised Design of Enantioselective Transfer Hydrogenation Catalysts

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Arene Complexes – an Odyssey Towards a Revised Design of Enantioselective Transfer Hydrogenation Catalysts Chiral ansa-Ligated Ruthenium(II) η6-Arene Complexes – An Odyssey towards a Revised Design of Enantioselective Transfer Hydrogenation Catalysts Den Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades vorgelegt von Immo Weber aus Tübingen - 1 - - 2 - Als Dissertation genehmigt von den Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität Erlangen-Nürnberg. Tag der mündlichen Prüfung: 29. Mai 2006 Vorsitzender der Promotionskommission: Prof. Dr. Donat-Peter Häder Erstberichterstatter: Prof. Dr. Ulrich Zenneck Zweiberichterstatter: Prof. Dr. Lutz Dahlenburg Drittberichterstatterin: Prof. Dr. Evamarie Hey-Hawkins (Universität Leipzig) - 3 - - 4 - Diese Arbeit widme ich in Dankbarkeit meiner Familie und all denjenigen Menschen, die mir in Freude und Leid Teil meines Lebens sind, die ich Freunde nennen darf und die ich nicht missen möchte. Amicus certus in re incerta cernitur! Dem Andenken an meine Großmutter Therese Ursula Nickolay, an meinen Großvater Hans-Joachim Weber, Herrn Dr. Wolf Harm, Ursula Heintzmann und Travis Moulton Das wirklich Gute eines Menschen offenbart sich darin, inwieweit er in unserem Herzen weiterlebt. „Unsere Jahre sind im Raum der Zeit nur ein kleines Teilchen, unser Leben ist im Raum der Zeit nur ein kleines Weilchen, unser Werk ist im Mosaik der Zeit vielleicht ein helles Steinchen“ Rudolf Burger - 5 - - 6 - Die vorliegende Arbeit wurde in der Zeit von Januar 2002 bis Februar 2005 am Institut für Anorganische Chemie II der Friedrich-Alexander-Universität Erlangen- Nürnberg unter der Anleitung von Herrn Prof. Dr. Ulrich Zenneck angefertigt. Mein Dank gilt Herrn Prof. Dr. Ulrich Zenneck für die Aufgabenstellung, für seine Förderung und für den großen Freiraum bei der Gestaltung dieser Arbeit. Herrn Prof. Dr. Lutz Dahlenburg danke ich für die freundliche Übernahme des Koreferats, Frau Prof. Dr. Evamaria Hey-Hawkins (Universität Leipzig) für das Drittgutachten, Herrn Prof. Dr. Hans H. Brand für die Nebenfachprüfung und Herrn Prof. Dr. Rolf Saalfrank für den Prüfungsvorsitz. Die Arbeiten über β-Aminothioether chelatisierte Ruthenium(II)-η 6-Arenkomplexe (Kapitel 3) widme ich dem Andenken an Herrn Prof. Dr. Dieter Sellmann. Sie beruhen auf seiner Initiative und wurden mir als ursprüngliches Thema meiner Dissertation von Herrn Prof. Dr. Ulrich Zenneck anvertraut. Für sehr weiterführende, äußerst motivierende und entscheidende Diskussionsbeiträge danke ich den Herren Prof. Dr. Walter Bauer, Prof. Dr. Henri B. Kagan (Université Paris-Sud, Frankreich), Prof. Dr. Antonio Togni (Eidgenössische Technische Hochschule Zürich, Schweiz), Dr. Frank Heinemann, Dr. Ralph Puchta, Dr. Guido Marconi (jetzt Università Pisa, Italien) und Dr. Wolfgang Utz. Dem Graduiertenkolleg "Homogener und Heterogener Elektronentransfer“ des Sonderforschungbereiches 583 der Deutschen Forschungsgemeinschaft danke ich für die Gewährung eines Stipendiums 2002 und dem Chemie Computer Centrum der Friedrich-Alexander-Universität Erlangen-Nürnberg für einen Gastaufenthalt 2003. Der Kunststoff- und Metallwarenfabrik GmbH & Co. KG Erlangen danke ich für die Teilzeiteinstellung ab Januar 2005, für die Chemikalienspenden zur Unterstützung des Ferrocenprojektes (Kapitel 5) und für die großzügige Übernahme der Druckosten der vorliegenden Dissertation. Der Firma Braun danke ich für die kontinuierlichen Spenden von Einwegspritzen. Bei den Herren Dr. Frank Heinemann und Panos Bakatselos bedanke ich mich für die vielen und häufig komplizierten Röntgenstrukturanalysen. Bei Herrn Prof. Dr. Walter Bauer, Herrn Dr. Achim Zahl, Herrn Dr. Matthias Moll und Herrn Bob O´Brien - 7 - bedanke ich mich für die zahlreichen und oft nicht routinemäßigen NMR-Messungen. Herrn Prof. Dr. Stefano Superchi (Università della Basilicata, Italien) danke ich für die Durchführung und Expertise der CD-Spektren der {[σ(P):η6-(Aren-ansa-phosphinit)]- ruthenium(II)aminokomplexe (Kapitel 4). Herrn Dr Konrad Szaciłowski (Wydział Chemii, Uniwersytet Jagielloński, Kraków, Polen) danke ich für CV-Messungen zur Klärung der notwendigen Bedingungen für eine erfolgreiche Umsetzung von Cyclohexadienderivaten zu Ruthenium(II)-η6-Arenkomplexen (Kapitel 5). Den Herren Prof. Dr. Andreas Hirsch und Prof. Dr. Peter Gmeiner danke ich, daß ich in ihren Arbeitskreisen alle polariemetrischen Messungen, die Aufnahme der CD-Spektren der β-Aminothioether chelatisierten Ruthenium(II)-η 6-Arenkomplexe (Kapitel 3) und sämtliche Schmelzpunktbestimmungen durchführen konnte. Frau Christina Wronna danke ich für die Durchführung der Elementaranalysen. Den Herren Dieter Wein und Hans Zöbelein danke ich für die Anfertigung als auch Reparatur von Glasgeräten. "Es ist die Aufgabe der Naturwissenschaften, durch eine wirkliche Einsicht in die Zusammenhänge der Natur dem Menschen die richtige Stellung in ihr zuzuweisen.“ Werner Heisenberg - 8 - Parts of this thesis were extracted as separate manuscripts planned to be published or are already submitted for publication: • Immo Weber, Frank W. Heinemann, Walter Bauer, Ulrich Zenneck; “Configurational Stability of Epimeric β-Aminothioether-Chelated Ruthenium(II) η6-Arene Complexes – Can it be controlled?”; to be published. • Immo Weber, Frank W. Heinemann, Walter Bauer, Stefano Superchi, Achim Zahl, Joanna Procelewska, Slawomir Procelewski, Daniela Richter, Ulrich Zenneck; "Structural Relaxation of Diastereomeric {[η6:σ(P)-(Arene-ansa- phosphinite)]Ruthenium(II) Amino} Cations under Configurational Stabilization of Chiral Ruthenium(II) Centers"; to be published. • Frank W. Heinemann, Immo Weber, Ulrich Zenneck; "Crystal structures of (-)- (SS, 1R, 2S, 5R)-menthyl p-tolyl sulfinate and (+)-(SS)-[(p-tolyl)sulfinyl]- ferrocene"; Journal of Chemical Crystallography, submitted. • Immo Weber, Frank W. Heinemann, Ulrich Zenneck; "A Synthesis Detour to Planar Diastereomeric Ferrocene Derivatives around an Unusual Rearrangement of ortho-Lithiated Kagan's Template (+)-(SS)-[(p-Tolyl)sulfinyl]- ferrocene ", to be published. • Immo Weber, Frank W. Heinemann, Panos Bakatselos, Ulrich Zenneck; "A Cornucopia of Catalysis Intermediates and Byproducts from a Stille Crosscoupling of a Planar Chiral Ferrocene", to be published. - 9 - - 10 - Contents Numbering and Nomenclature of Compounds Abbreviations Zusammenfassung....................................................................................1 Abstract..........................................................................................................5 1 Theoretical Background....................................................................9 1.1. Chirality…………………………………………………………………….....9 1.2. Pseudopolyhedral hapto-Arene Complexes with Chiral Metal Centers……………………………………………….....19 1.3. Principles of Enantioselective Catalysis exemplified on CaTHy Reactions..............................................................................................23 1.4. Catalysts Design for Enantioselective Ketone Hydrogenation by the Octant Rule…………………………………………….…………….....40 1.5. Anticipated Use of Chiral ansa-Ligated Ruthenium(II) η6-Arene Complexes as THy Catalysts…………………………………..……...….54 1.6. Chiral ansa-Thioether Ru(II) η6-Arene THy Catalysts as initial goal of this work………………………………………………...……67 2 Preexperiments.....................................................................................73 2.1 Ruthenium(II) η6-Benzene Precursor Complexes…………………...….73 2.2. Synthesis Attempts of ansa-Thioether and ansa-Thiolato Ruthenium(II) η6-Arene Complexes ……….……………………...……..77 3 Preparation and Study of Epimeric β-Aminothioether- 6 Chelated Ruthenium(II) η -Arene Complexes....................82 3.1 Synthesis of Chiral β-Aminothioether Ligands…… …………...........…85 3.2 Epimeric σ(N):σ(S)-β-Aminothioether Ruthenium(II) η6-Arene Complexes.............................................................................95 - 11 - 4 Preparation and Study of Diastereomeric {[σ(P):η6- (Arene-ansa-Phosphinite)] Ruthenium(II) Amino} Complexes............................................................................................121 4.1 Synthesis............................................................................................122 4.2 Circular Dichroism Study....................................................................143 4.3 NMR Study and Epimerization Barrier................................................146 4.4 Catalytic Experiments and Conclusions.............................................156 5 Revised Design of Enantioselective ansa-Ligated Ru(II) η6-Arene THy Catalysts - Outlook towards Planar Chiral ansa-Ferrocenyl Ligands..............................................162 5.1 Precursors and Reagents...................................................................165 5.2 Synthesis of and ortho Lithiation Studies with Kagan's Template......169 5.3 Towards a Racemic {σ(N):η6-[1-(2'-aminomethylferrocenyl)- benzene]} Ruthenium(II) Complex......................................................178 6 Conclusion and Closing Remarks..........................................188 7 Experimental Part..............................................................................189 7.1. Materials and Methods........................................................................189 7.2. Precursor Compounds........................................................................194 7.2.1 General Procedure for Birch Reductions............................................194 1-Methoxycarbonylcyclohexa- 2, 5-diene 3........................................ 195 1,3,5-Trimethylcyclohexa-1,4-diene
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