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Functionalization of Arenes and Heteroarenes by Metalation with Tmp-Bases Or Metal Insertion

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Functionalization of Arenes and Heteroarenes by Metalation with Tmp-Bases Or Metal Insertion Dissertation zur Erlangung des Doktorgrades der Fakultät für Chemie und Pharmazie der Ludwig-Maximilians-Universität München FUNCTIONALIZATION OF ARENES AND HETEROARENES BY METALATION WITH TMP-BASES OR METAL INSERTION AND SYNTHESIS OF TETRASUBSTITUTED ALKENYL SULFIDES VIA A CU(I)- MEDIATED CARBOMETALATION von Cora Dunst aus Starnberg 2011 Erklärung Diese Dissertation wurde im Sinne von § 13 Abs. 3 bzw. 4 der Promotionsordnung vom 29. Januar 1998 (in der Fassung der sechsten Änderungssatzung vom 16. August 2010) von Herrn Prof. Dr. Paul Knochel betreut. Ehrenwörtliche Versicherung Diese Dissertation wurde selbständig, ohne unerlaubte Hilfe erarbeitet. München, den 29.07.2011 ............................................. Cora Dunst Dissertation eingereicht am 3.08.2011 1. Gutachter: Prof. Dr. Paul Knochel 2. Gutachter: Prof. Dr. Manfred Heuschmann Mündliche Prüfung am 13.09.2011 TO MY PARENTS & GRANDPARENTS This work was carried out from May 2008 to June 2011 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 thank Prof. Dr. Paul Knochel for giving me the opportunity to do my Ph.D. in his group, for his generous support and guidance in the course of my scientific research. I am also grateful to Prof. Dr. Manfred Heuschmann for agreeing to be the second reviewer of this thesis, as well as Prof. Dr. Konstantin Karaghiosoff, Prof. Dr. Herbert Mayr, Prof. Dr. Heinz Langhals and Prof. Dr. Thomas Bein for their interest shown in the manuscript by accepting to be referees. I really would like to thank Dr. Laurin Melzig, Thomas Kunz, Nadja Barl and Sebastian Bernhardt for the careful correction of this manuscript. Thanks to all the past and present members who created a great (working) atmosphere. I want to thank especially Andy Wagner, Andi Unsinn, Gabriel Monzon, Andi Steib, Christoph Sämann, Marcel Kienle, and Dr. Stefan Wunderlich for being the best lab mates one could imagine. I thank Dr. Laurin Melzig for his help and great times during our coffee breaks and Dr. Silvia Zimdars and Dr. Tomke Bresser for the funny times we had during our lunch-“Rewe”-breaks. Thanks go to Dr. Albrecht Metzger, Dr. Marcel Kienle, Gabriel Monzon, Dr.Tomke Bresser and Dr. Stefan Wunderlich for the fruitful collaborations. I would also like to thank Renate Schröder, Dr. Vladimir Malakhov, Simon Matthe and Yulia Tsvik for their help in organizing everyday life in the office and in the lab, as well as the analytical team of the LMU for their invaluable help. Special thanks go to my family and to the best friends in the world for their tremendous support throughout my studies and my PhD. I couldn’t have done this without you. Finally I would like to thank Boris for his love and encouragement even through rainy days. Parts of this Ph.D. thesis have been published: 1. Cora Dunst, Albrecht Metzger, Elena Zaburdaeva, Paul Knochel, „Stereoselective Synthesis of Polyfunctional Tetrasubstituted Alkenyl Thioethers via a Carbocupration of Alkynyl Sulfides with Aryl and Benzylic Diorganozincs“, Synthesis, accepted. 2. Cora Dunst, Paul Knochel, „Regioselective Functionalization of the Thiazole Scaffold using TMPMgCl∙LiCl and TMP2Zn·2MgCl2·2LiCl”, J. Org. Chem. 2011, 76, 6972. 3. Cora Dunst, Paul Knochel, „Selective Mg Insertion into Substituted Mono- and Di-Chloro Arenes in the Presence of LiCl. A new Preparation of Boscalid”, Synlett 2011, 14, 2064. 4. Marcel Kienle, Andreas J. Wagner, Cora Dunst, Paul Knochel, „Preparation of Heterocyclic Amines by an Oxidative Amination of Zinc Organometallics Mediated by CuI: A New Oxidative Cycloamination for the Preparation of Annulated Indole Derivatives” Chem. Asian J. 2011, 6, 517. 5. Stefan Wunderlich, Tomke Bresser, Cora Dunst, Gabriel Monzon, Paul Knochel, „Efficient Preparation of Polyfunctional Organometallics via Directed ortho-Metalation”, Synthesis 2010, 15, 2670. 6. Cora Dunst, Marcel Kienle, Paul Knochel, „Preparation of Heterocyclic Amines via a Copper(I)-Mediated Oxidative Cross-Coupling of Organozinc Reagents with Lithium Amides”, Synthesis 2010, 13, 2313. 7. Marcel Kienle, Cora Dunst, Paul Knochel, „Oxidative Amination of Heteroaromatic Zinc Reagents Mediated by PhI(OAc)2”, Org. Lett. 2009, 11, 5158, selected for Synfacts 2010, 2, 213, selected in „Highlights, C-H Functionalization”, Angew. Chem. Int. Ed. 2010, 49, 2 A. INTRODUCTION ...........................................................................................................................13 1. Overview ....................................................................................................................................15 2. General Preparation of Organomagnesium or Organozinc Reagents .....................................16 2.1. Metal Insertion .............................................................................................................................16 2.2. Halogen-Metal Exchange Reactions .............................................................................................19 2.3. Directed Metalations ....................................................................................................................21 3. Amination Reactions ..................................................................................................................25 3.1. Transition Metal Catalyzed Amination Reactions .........................................................................25 3.2. Oxidative Amination Reactions ....................................................................................................26 4. Carbometalation Reactions .......................................................................................................28 5. Objectives ...................................................................................................................................32 B. RESULTS AND DISCUSSIONS ....................................................................................................35 1. Regioselective Functionalization of the Thiazole Scaffold using TMPMgCl·LiCl and TMP2Zn·2MgCl2·2LiCl .............................................................................................................37 1.1. Introduction .................................................................................................................................37 1.2. Results and Discussions ...............................................................................................................38 1.2.1. Functionalization of the Thiazole Scaffold at the 5-Position .........................................................39 1.2.2. Functionalization of the Thiazole Scaffold at the 4-Position .........................................................41 1.2.3. Deprotection of the TMS-Group with Bu4NF or ICl .....................................................................45 1.2.4. Further Functionalization of the Thiazole Scaffold .......................................................................46 2. Oxidative Amination of Heteroaromatic Zinc Reagents Mediated by PhI(OAc)2 ...................48 2.1. Introduction .................................................................................................................................48 2.2. Results and Discussions ...............................................................................................................49 2.2.1. Oxidative Amination of Zincated Heterocycles Obtained by Metalation with TMP2Zn·2MgCl2·LiCl .................................................................................................................49 2.2.2. Oxidative Amination of Zincated Heterocycles Obtained by Mg Insertion in the Presence of LiCl and ZnCl..........................................................................................................................51 2.2.3. Oxidative Amination of Zincated Heterocycles in Large Scale .....................................................53 3. Efficient Preparation of Polyfunctional Organometallics Via Directed Ortho-Metalation Using TMP-Bases of La, Mn and Fe..........................................................................................55 3.1. Introduction .................................................................................................................................55 3.2. Results and Discussion .................................................................................................................56 4. Selective Mg Insertion into Substituted Mono- and Di-Chloro Arenes in the Presence of LiCl. A new Preparation of Boscalid. ....................................................................................59 4.1. Introduction .................................................................................................................................59 4.2. Results and Discussions ...............................................................................................................60 5. Stereoselective Synthesis of Polyfunctional Tetrasubstituted Thioethers via a Carbocupration of Alkynyl Sulfides with Aryl and Benzylic Diorganozincs ...........................65 5.1. Introduction .................................................................................................................................65 5.2. Results and Discussions ...............................................................................................................65 5.2.1. Carbocupration of Thioether-Substituted Alkynes ........................................................................65
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