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Sulfoxide-Controlled Functionalization of Arenes and Heterocycles, Transition Metal-Catalyzed Cross-Coupling Reactions of Thioet

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Sulfoxide-Controlled Functionalization of Arenes and Heterocycles, Transition Metal-Catalyzed Cross-Coupling Reactions of Thioet Dissertation zur Erlangung des Doktorgrades der Fakultät für Chemie und Pharmazie der Ludwig-Maximilians-Universität München Sulfoxide-Controlled Functionalization of Arenes and Heterocycles Transition Metal-Catalyzed Cross-Coupling Reactions of Thioethers Chlorine-Zinc Exchange Reactions Laurin Melzig aus Starnberg 2011 Erklärung Diese Dissertation wurde im Sinne von § 13 Abs. 3 bzw. 4 der Promotionsordnung vom 29. Januar 1998 von Herrn Prof. Dr. Paul Knochel betreut. Ehrenwörtliche Versicherung Diese Dissertation wurde selbständig, ohne unerlaubte Hilfe bearbeitet. München, am 21. Januar 2011 …..…………………………………… Laurin Melzig Dissertation eingereicht am 25. Januar 2011 1. Gutachter: Prof. Dr. Paul Knochel 2. Gutachter: Prof. Dr. Manfred Heuschmann Mündliche Prüfung am 3. März 2011 This work was carried out from March 2007 to December 2010 under the guidance of Prof. Dr. Paul Knochel at the Department Chemie und Pharmazie of the Ludwig-Maximilians- Universität, Munich. First, I would like to express my appreciation to Prof. Dr. Paul Knochel for giving me the great opportunity to do my Ph.D. in his group and for his guidance and support in the course of my scientific research. I am also very grateful to Prof. Dr. Manfred Heuschmann for agreeing to be my “Zweitgutachter” as well as Prof. Dr. Heinz Langhals, Prof. Dr. Klaus Wanner, Prof. Dr. Konstantin Karaghiosoff and Prof. Dr. Rudolf Knorr for their interest shown in this manuscript by accepting to be referees. Furthermore, I would like to express my gratitude to Andreas Wagner, Sebastian Bernhardt, and Dr. Coura Diène for the careful correction of this manuscript. I thank all past and present co-workers I have met in the Knochel group for their kindness, their help in every respect and the good times we had. Special thanks to my actual and former lab mates Zhihua Peng, Zhi-Liang Shen, Dr. Anukul Jana, Dr. Georg Manolikakes, Dr. Shigeyuki Yamada, Dr. Carmen Muñoz Hernández, Camille Gignoux, Kohsuke “Baba” Kawabata and Prof. Kimihiro Komeyama and last but the most: Dr. “cumon” Andrei Gavryushin. I would like to bow to Dr. Christian Rauhut for the fruitful collaboration in the field of sulfoxide chemistry and nerdism, Dr. Albrecht Metzger and Dr. Christina Despotopoulou for their work on the thiomethyl cross-coupling reactions and the very bad or rather very good influence on my manners (συγγνώµη !), and Dr. Coura Diène for her great patience with the hard road of our chlorine-zinc exchange and for making me blush. I would also like to thank Vladimir Malakhov, Simon Matthe, Renate Schröder and Yulia Tsvik for their help in organizing everyday life in the lab and in the office, as well as the analytical team of the LMU for their invaluable help. Sincere props to Niko Naredi-Rainer, Teresa Dennenwaldt, and Jérémy Stemper for easing up the lab work in course of their internships in the Knochel group. I would like to thank my family and my friends for their great support, throughout my studies and my Ph.D. Finally, I thank Marilena for her never-ending love and only rarely ending patience with me. Parts of this Ph.D. thesis have been published 1) Christian B. Rauhut, Laurin Melzig and Paul Knochel, „ Meta - and para - Difunctionalization of Arenes via a Sulfoxide-Magnesium Exchange Reaction”, Org. Lett . 2008 , 10 , 3891. 2) Laurin Melzig, Christian B. Rauhut, and Paul Knochel, „ Meta - and para - Difunctionalization of Arenes via an ortho -Magnesiation and a Subsequent Sulfoxide- Magnesium Exchange”, Synthesis 2009 , 6, 1041. 3) Laurin Melzig, Christian B. Rauhut, and Paul Knochel, „2,3-Functionalization of Furans, Benzofurans and Thiophenes via Magnesiation and Sulfoxide-Magnesium Exchange”, Chem. Commun . 2009 , 24 , 3536, selected as „Hot Article”. 4) Albrecht Metzger, Laurin Melzig, Christina Despotopoulou and Paul Knochel, „Pd- Catalyzed Cross-Coupling of Functionalized Organozinc Reagents with Thiomethyl- Substituted Heterocycles”, Org. Lett. 2009 , 11 , 4228, selected for Synfacts 2009 , 12 , 1384, selected in „Highlights from the literature”, Org. Process Res. Dev. 2010 , 14 , 2. 5) Laurin Melzig, Albrecht Metzger and Paul Knochel, „Ni-Catalyzed Cross-Coupling of Functionalized Organozinc Reagents with Thiomethyl-Substituted Heterocycles”, J. Org. Chem. 2010 , 75 , 2131 . 6) Laurin Melzig, Jeremy Stemper and Paul Knochel, „A novel Palladium-Catalyzed Cross- Coupling of Thiomethylated Alkynes with Functionalized Organozinc Reagents”, Synthesis 2010 , 12 , 2085 . 7) Albrecht Metzger, Laurin Melzig and Paul Knochel, „Up-Scaled Transition Metal- Catalyzed Cross-Couplings of Thioether-Substituted N-Heterocycles with Organozinc Reagents”, Synthesis 2010 , 16 , 2853. 8) Laurin Melzig, Albrecht Metzger and Paul Knochel, „Pd- and Ni-catalyzed Cross-Coupling Reactions of Functionalized Zinc Reagents with Thioethers”, Chem Eur. J. 2011 , 17 , 2948 . 9) Laurin Melzig, Christian B. Rauhut, Niko Naredi-Rainer and Paul Knochel, „Difunctionalization of Arenes and Heteroarenes via a Sulfoxide-Magnesium Exchange Reaction”, Chem Eur. J., ASAP . 10) Laurin Melzig, Coura R. Diène, C. J. Rohbogner and Paul Knochel, „Preparation of Polyfunctional Zinc Organometallics using a Fe- or Co-Catalyzed Cl/Zn-Exchange”, Angew. Chem. Int. Ed., submitted. To Marilena Don't walk behind me; I may not lead. Don't walk in front of me; I may not follow. Just walk beside me and be my friend. Albert Camus Table of Contents A. Introduction .................................................................................................................... 11 1. General Introduction ....................................................................................................................... 11 2. Halogen-Metal Exchange Reactions ......................................................................................... 14 3. Other Metal Exchange Reactions .............................................................................................. 19 4. Metalation Reactions .................................................................................................................. 23 5. Cross-Coupling Reactions of Organometallics with Unsaturated Thioethers ....................... 28 6. Objectives .................................................................................................................................... 31 B. Results and Discussion .................................................................................................. 34 1. Preparation of 1,2,4-Trisubstituted Arenes via DoM and Sulfoxide-Magnesium Exchange 34 1.1 Synthetic Strategy ..................................................................................................................... 34 1.2 Preparation of Diaryl Sulfoxides ............................................................................................... 35 1.3 Ortho-Metalation of Diaryl Sulfoxides ...................................................................................... 36 2. Preparation of Functionalized 5-Membered Heterocycles via D oM and Sulfoxide- Magnesium Exchange ..................................................................................................................... 50 2.1 Synthetic Strategy and Preparation of Hetaryl Sulfoxides ............................................................ 50 2.2 Ortho-Metalation and Sulfoxide-Magnesium Exchange on 5-Membered Hetaryl Sulfoxides .......... 52 2.3 Full Functionalization of Thiophene by Metalation Reaction ....................................................... 54 3. Preparation of Disubstituted Pyridines via D oM, Sulfoxide-Magnesium Exchange and Ligand Coupling .............................................................................................................................. 56 3.1 Synthetic Strategy and Preparation of Pyridinyl Sulfoxides ........................................................... 56 3.2 Preparation of 3,4-Disubstituted and Tetrasubstituted Pyridines .................................................. 57 3.3 Ligand Coupling reactions of 2-Pyridinyl Sulfoxides ................................................................... 59 3.4 Preparation of a Cyclooxygenase-2 Inhibitor using the Ligand Coupling Reaction .......................... 60 4. Transition Metal-Catalyzed Cross-Coupling Reactions of Functionalized Organozinc Reagents with Unsaturated Thioethers ......................................................................................... 61 4.1 Synthetic Goals and Synthesis of Unsaturated N-Heterocyclic and Alkynyl Thioethers .................. 61 4.2 Optimization of the Pd-Catalyzed Cross-Coupling Reaction of N-Heterocyclic Thioethers .............. 62 4.3 Synthesis of Functionalized N-Heterocycles via Pd-Catalyzed Cross-Coupling Reactions ................ 63 4.4 Optimization of the Ni-Catalyzed Cross-Coupling Reaction of N-Heterocyclic Thioethers .............. 66 4.5 Synthesis of Functionalized N-heterocycles via Ni-catalyzed Cross-Coupling Reactions ................... 68 4.6 Large Scale Preparation of Functionalized N-Heterocycles via Cross-Coupling Reactions ............... 72 4.7 Pd-Catalyzed Cross-Coupling Reactions of Thiophenylated Heterocycles ........................................ 73 4.8 Optimization of Conditions for the Synthesis of Functionalized Alkynes via Cross-Coupling Reactions ..................................................................................................................................................... 74 4.9 Synthesis of Functionalized Alkynes via Pd-catalyzed Cross-Coupling
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