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New Applications of the Borrowing Hydrogen Methodology - Selective Synthesis of Amines and Mechanistic Studies“

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New Applications of the Borrowing Hydrogen Methodology - Selective Synthesis of Amines and Mechanistic Studies“ NEW APPLICATIONS OF THE BORROWING HYDROGEN METHODOLOGY - SELECTIVE SYNTHESIS OF AMINES AND MECHANISTIC STUDIES Dissertation zur Erlangung des akademischen Grades eines Doktor rerum naturalium (Dr. rer. nat.) vorgelegt der Mathematisch–Naturwissenschaftlichen Fakultät der Universität Rostock von Dirk Hollmann geb. am 02.05.1977 Rostock, Juli 2008 urn:nbn:de:gbv:28-diss2009-0012-1 Das Schönste am Leben ist das Lachen seines Kindes. Für Nadine und Tobias Die vorliegende Arbeit wurde unter der Leitung von Herrn Prof. Dr. Matthias Beller in der Zeit von Februar 2006 bis Juli 2008 am Leibniz–Institut für Katalyse e.V. an der Universität Rostock angefertigt. Gutachter: Prof. Matthias Beller (Leibniz-Institut für Katalyse e.V. an der Universität Rostock) Prof. Jonathan M. J. Williams (University of Bath, UK) Prof. Lutz Ackermann (Universität Göttingen) Abgabedatum: 01. August 2008 Herrn Prof. Dr. Matthias Beller danke ich für die hervorragenden Arbeitsbedingungen, die interessante Fragestellung und die tatkräftige Unterstützung. Besonders der Enthusiasmus bezüglich der Chemie und die darauf aufbauenden Diskussionen waren und werden mir immer eine Hilfe und ein Vorbild sein. Weiterhin gilt mein besonderer Dank den Mitgliedern der Projektgruppe „Katalytische Wirkstoffsynthesen“, die einen maßgeblichen Anteil am Gelingen dieser Arbeit hatten: Meiner Themenleiterin Frau Dr. Annegret Tillack für die ausgezeichnete und freundschaftliche Zusammenarbeit während der letzten Jahre, Karolin Alex, Sebastian Bähn und Sebastian Imm für ihre Freundschaft, die täglichen Diskussionen, Anregungen und die Zusammenarbeit, Kathleen Mevius für die hervorragende Zusammenarbeit im Labor, weiterhin Nicolle Schwarz, Dr. Anahit Pews-Davtyan und Dr. Dirk Michalik. Dr. Rudy Parton und Dr. Rinke Altink vom Kooperationspartner DSM danke ich für die interessante Aufgabenstellung sowie für die ausführlichen Diskussionen und ihre Hilfe, die den Erfolg dieser Arbeit erst ermöglichten. Allen Freunden und Kollegen danke ich für ihre Unterstützung, Diskussionen, Chemikalien und die hervorragende Arbeitsatmosphäre: Daniele Addis, Bianca Bitterlich, Anne Brennführer, Cathleen Buch, Dr. Stephan Enthaler, Giulia Erre, Christian Fischer, Sandra Giertz, Anne Grotevendt, Hanns- Martin Kaiser, Björn Loges, Irene Piras, Henry Postleb, Angelika Preetz, Thomas Schmidt, Kristin Schröder, Stefan Schulz, Thomas Schulz, Jan Schumacher, Christian Torborg, Bianca Wendt und Gerrit Widenhöfer, insbesondere der Zocker-Bande: Albert Boddien, Reiko Jennerjahn, Lorenz Neubert, Stefan Peitz und Sebastian Bähn, sowie Dr. Ralf Jackstell, Dr. Henrik Junge, Dr. Katrin Junge, Dr. Helfried Neumann, Dr. Alexander Zapf, Dr. Hajun Jiao, Dr. Irina Jovel, Dr. Thomas Schareina, Dr. Holger Klein, Dr. Alexey Sergeev, Dr. Man Kin Tse und vielen mehr. Dr. Torsten Dwars für die schnelle und unkomplizierte Chemikalienbeschaffung. Dem Analytik-Team des Leibniz–Instituts für Katalyse: Andreas Koch für die unzähligen und langen NMR-Messungen, Dr. Christine Fischer, Dr. Anke Spanneberg, Dr. Wolfgang Baumann, Susanne Schareina, Astrid Lehmann, Kathrin Reincke, Anja Kammer und Susann Buchholz für die Messung unzähliger GC–Proben. Daniela Voigtländer danke ich für die hervorragende Beratung und Überprüfung der englischsprachigen Publikationen. Mein besonderer Dank gilt meinen Eltern und meiner Schwester und Ihrer Familie, meinen Freunden und meiner Lebenspartnerin Nadine sowie meinem Sohn Tobias, ohne die diese Arbeit nicht möglich gewesen wäre. List of Publications This thesis is based on the following papers, referred to in the captions by their Roman numerals I-IX. I A Novel Ruthenium-catalyzed Amination of Primary and Secondary Alcohols. Annegret Tillack, Dirk Hollmann, Dirk Michalik, and Matthias Beller, Tetrahedron Lett. 2006, 47, 8881-8885. II An Improved Ruthenium Catalyst for the Environmentally Benign Amination of Primary and Secondary Alcohols. Dirk Hollmann, Annegret Tillack, Dirk Michalik, Ralf Jackstell, and Matthias Beller, Chem. Asian J. 2007, 3, 403-410 (VIP paper with front cover). III Salt-free Synthesis of Tertiary Amines via Ruthenium-catalyzed Amination of Alcohols. Annegret Tillack, Dirk Hollmann, Kathleen Mevius, Dirk Michalik, Sebastian Bähn, and Matthias Beller, Eur. J. Org. Chem. 2008, 4745-4750. IV A General Ruthenium-catalyzed Synthesis of Aromatic Amines. Dirk Hollmann, Sebastian Bähn, Annegret Tillack, and Matthias Beller, Angew. Chem. Int. Ed. 2007, 46, 8291-8294, Angew. Chem. 2007, 119, 8440-8444 (Hot Paper). V N-Dealkylation of Aliphatic Amines and Selective Synthesis of Monoalkylated Aryl Amines. Dirk Hollmann, Sebastian Bähn, Annegret Tillack, and Matthias Beller, Chem. Commun. 2008, 3199-3201. VI Ruthenium-catalyzed Synthesis of Secondary Alkylamines: Selective Alkylation with Aliphatic Amines. Sebastian Bähn, Dirk Hollmann, Annegret Tillack, and Matthias Beller, Adv. Synth. Cat. 2008, 350, 2099-2103. VII A Novel Salt-free Ruthenium-catalyzed Alkylation of Aryl Amines. Dirk Hollmann, Sebastian Bähn, Annegret Tillack, Rudy Parton, Rinke Altink, and Matthias Beller, Tetrahedron Lett. 2008, 49, 5742-5745. VIII Pyrrolidine Activation: C–N Bond Cleavage and Formation and New Mechanistic Aspects in the Activation of the Shvo Catalyst. Dirk Hollmann, Rudy Parton, Rinke Altink, Annegret Tillack, Sebastian Bähn, Anke Spannenberg, Haijun Jiao, and Matthias Beller, Organometallics 2008, submitted for publication. IX Deactivation of the Shvo Catalyst by Ammonia: Synthesis, Characterization and Modeling. Dirk Hollmann, Haijun Jiao, Anke Spannenberg, Sebastian Bähn, Annegret Tillack, Rudy Parton, Rinke Altink, and Matthias Beller, Organometallics 2008, accepted for publication. Abstract This cumulative thesis deals with the application of the Borrowing Hydrogen methodology in organic synthesis. This concept combines the dehydrogenation and hydrogenation with numerous of organic transformations. The introduction gives an overview of the current research in the area of Borrowing Hydrogen, which expands from activation of C-C bonds to C-O bonds and finally to C-N bonds. During my research, the Borrowing Hydrogen methodology was applied in the synthesis of secondary and tertiary amines starting from secondary alcohols by C- O activation. Furthermore, I was able to introduce the selective synthesis of monoalkylated aryl amines using primary, secondary, and tertiary amines by C-N activation. This new method was continuously applied in the alkylation of t-alkyl amines. Additionally, mechanistic studies in the activation and deactivation of the Shvo catalyst (2) were performed. The results of my work, reported in the publications I-IX listed on the preceding page, are integrated and associated with state-of-the-art chemistry in this field. My ambition is to help the reader to get interested in this field and to understand these transformations. I also want to emphasize the work I have been responsible for. Zusammenfassung Diese kumulative Dissertation befasst sich mit der Anwendung der Borrowing Hydrogen (Ausleihen von Wasserstoff) Methodik in der organischen Synthese. Dieses Konzept kombiniert die Schritte der Hydrierung und Dehydrierung mit einer Vielzahl von organischen Reaktionen. Die Einleitung gibt einen Überblick über die aktuelle Forschung auf dem Gebiet der Borrowing Hydrogen Methodik. Diese umfasst die Aktivierung von C-C Bindungen, C-O Bindungen sowie von C-N Bindungen. In meiner Forschung wurde diese Methodik in der Synthese von sekundären sowie tertiären Aminen mittels sekundärer Alkohole angewandt. Weiterhin befasste ich mich mit der selektiven Synthese von monoalkylierten Aryl aminen. Dabei konnten primäre, sekundäre sowie tertiäre Alkyl amine eingesetzt werden. Diese neue Methode wurde ebenfalls in der Alkylierung von t-Alkyl aminen angewandt. Zusätzlich zur organischen Synthese befasste ich mich mit mechanistischen Studien zur Aktivierung sowie Deaktivierung des eingesetzten Shvo Katalysators (2). Die Ergebnisse meiner Forschung, welche in den Publikationen I-IX auf den vorherigen Seiten aufgelistet sind, wurden in diese Übersicht integriert und mit der aktuellen Forschung auf diesem Gebiet verknüpft. Mein Bestreben mit dieser Arbeit ist es, das Interesse für dieses sehr interessante Gebiet sowie ein Verständnis für die damit möglichen Reaktionen in der organischen Chemie zu wecken. Abbreviations BINAP 2,2'-Binaphtyldiphenyldiphosphine Bn Benzyl Bu Butyl CO Carbonyl cod Cyclooctadien Cp* Pentamethylcyclopentadienyl DME Dimethoxyethane DMSO Dimethylsulfoxide dppf 1,1'-Bis(diphenylphosphino)ferrocene dppp 1,3-Bis(diphenylphosphino)propane ee enantiomeric excess E-factor Environmental Factor Et Ethyl et al. et alia ip-foxap (S,S)-[2-(4'-Isopropyloxazolin-2'-yl)ferrocenyl]diphenylphosphine i- iso- Me Methyl MPV Meerwein-Pondorf-Verley reduction Ph Phenyl Pr Propyl Py Pyridinium R Alkyl-, Aryl moiety t- tert- THF Tetrahydrofurane TsDPEN Tosyldiphenylethylendiamine Xantphos 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene Table of Contents List of Publications Abstract Zusammenfassung Abbreviations 1. Introduction ................................................................................................................ 1 1.1. Transfer Hydrogenation 1 2.Borrowing Hydrogen Methodology ...........................................................................5 2.1. Principles of the Borrowing Hydrogen Methodology 5 2.2. Activation of C-C Bonds 6 2.2.1. Alkane Metathesis 6 2.3. Activation of C-O Bonds 8 2.3.1. Aldol Condensation 8 2.3.2. -Bromination of Alcohols 10 2.3.3. Knoevenagel
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