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New Preparation of Polysubstituted Allenes, Benzylic Manganese Chlorides and Protected Aldol Products

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New Preparation of Polysubstituted Allenes, Benzylic Manganese Chlorides and Protected Aldol Products Dissertation zur Erlangung des Doktorgrades der Fakultät für Chemie und Pharmazie der Ludwig-Maximilians-Universität München New Preparation of Polysubstituted Allenes, Benzylic Manganese Chlorides and Protected Aldol Products. Transition Metal Free Benzylation of Unsaturated Cyanides. von Pauline Alice Quinio aus Saint Brieuc, France 2015 Erklärung Diese Dissertation wurde im Sinne von § 7 der Promotionsordnung vom 07. Oktober 2011 von Herrn Professor Dr. Paul Knochel betreut. Eidesstattliche Versicherung Diese Dissertation wurde eigenständig und ohne unerlaubte Hilfe bearbeitet. München, 29. Mai 2015 …..…………………………………… Pauline Alice Quinio Dissertation eingereicht am: 08. Juni 2015 1. Gutachter: Prof. Dr. Paul Knochel 2. Gutachter: Prof. Dr. Konstantin Karaghiosoff Mündliche Prüfung am: 29. Juni 2015 This work was carried out from October 2011 to March 2015 under the guidance of Prof. Dr. Paul Knochel at the Department of Chemistry at the Ludwig-Maximilians-Universität Munich. First of all, I would like to thank Prof. Dr. Paul Knochel for giving me the great opportunity to carry out my PhD thesis in his group, for his support and advice in the course of my scientific research and his interest in this work. I also would like to express my gratitude to Prof. Dr. Konstantin Karaghiosoff for agreeing to be second reviewer of this thesis and I thank all members of my defense committee – Prof. Dr. Manfred Heuschmann, Dr. Thomas Magauer, Prof. Dr. Franz Bracher, and Prof. Dr. Heinz Langhals – for their interest shown in this manuscript by accepting to be referees. I am really grateful to Dr. Dorian Didier, Mario Ellwart, Dr. Ilya Makarov, Julia Nafe and Dr. Daniela Sustac Roman for the carefull correction of this manuscript. I thank every member of the group that I met during my thesis for making this group “breathing” towards activities, meals and parties. Thank you to the best colleagues ever Dr. Annette Frischmuth and Dr. Sophia Manolikakes, we had so much nice moments in and outside the lab. Thanks again to you Annette and Vroni for the very nice trip to Paris. Special thank also goes to my french guys Dr. Dorian Didier and Sarah Fernandez. Thank you for encouraging me and keeping me smiling and laughing, I appreciate our common bad humor. I deeply thank my labmates in F2.004, for the interesting discussions and the really nice atmosphere: Dr. Sebastian Bernhardt, Peter Dowling, Dr. Christos Stathakis, Dr. Daniela Sustac Roman, Dr. Veronika Werner and Shen Zhi-liang. You made this lab full of life and I appreciate you let me sing and wisthle so bad than I can. I would like to thank Dr. Cyril François, Dr. Thierry León and Dr. Daniela Sustac Roman for the great collaborations, without forgetting my students Andreas Benischke, Jakob Gaar, Laura Kohout and Sharankini William, I wish you all success and luck in your future scientific research. Laura, I will never thank you enough for your kindness and comprehension, all my thesis long, vielen lieben Dank! I thank also, Dr. Sebastian Bernhardt, Dr. Tobias Blümke, Dr. Annette Frischmuth, Dr. Thomas Kunz, Dr. Albrecht Metzger and Theresa, Dr. Roland Appel and Claudia for the nice time I had with you on my free time. Thank you to Peter Dowling, Sophie Hansen, Dr. Vladimir Malakhov and Yulia Tsvik for their huge helps organizing everyday life in the lab and the office. Vladimir, it would now be right to say “Au revoir Monsieur”. Un très grand merci à mes parents et ma famille pour leur soutien et simplicité, la Bretagne me manque! Je remercie mes amis de Saint Brieuc, mes iutiens de Rennes et mes iupiens de Nantes pour leurs lointains mais pas moindre encouragements tout au long de ma thèse et plus particulièrement Luce et Chris, vous êtes des amours! Endlich, bedanke ich mich vor allem bei dir, Basti, für deine wahnsinnige Unterschützung. Du bist der beste und liebste Mensch , und unser Treffen bleibt mir die schönste Erinnerung dieser Zeit. Parts of this PhD thesis have been published 1. Sc(OTf) 3-Catalysed Addition of Bromomagnesium 2-Vinyloxy Ethoxide to Various Aldehydes leading to Protected Aldol Products P. Quinio , L. Kohout, D. Sustac Roman, J. Gaar, K. Karaghiosoff, P. Knochel, 2015 manuscript in preparation. 2. Transition Metal Free Cross-coupling of Aryl and N-Heteroaryl Cyanides with Benzylic Zinc Reagents P. Quinio , D. Sustac Roman, T. León, S. William, K. Karaghiosoff, P. Knochel, 2015 manuscript submitted. 3. Preparation of Tri- and Tetra-substituted Allenes via Regioselective Lateral Metalation of Benzylic Trimethylsilyl-Alkynes Using TMPZnCl·LiCl P. Quinio , C. François, A. Escribano Cuesta, A. K. Steib, F. Achrainer, H. Zipse, K. Karaghiosoff, P. Knochel, Org. Lett. 2015 , 17 , 1010. 4. New preparation of benzylic manganese chlorides by the direct insertion of magnesium into benzylic chlorides in the presence of MnCl 2·2LiCl P. Quinio , A. D. Benischke, A. Moyeux, G. Cahiez, P. Knochel Synlett 2015 , 26 , 514. 5. BF 3-Mediated Oxidative Cross-Coupling of Pyridines with Alkynyllithium Reagents and Further Reductive Functionalizations of the Pyridine Scaffold T. León, P. Quinio , Q. Chen, P. Knochel Synthesis 2014 , 46 , 1374. À mes parents Annick et Pierre Et mes soeurs Aurélie et Sandrine “La chance, c’est comme le Tour de France: on l’attend et ça passe vite.” Dialogue du film Le fabuleux Destin d’Amélie Poulain , de Jean-Pierre JEUNET TABLE OF CONTENTS TABLE OF CONTENTS Introduction ................................................................................................................................ 1 I. Overview ........................................................................................................................ 2 II. Preparation of organometallic reagents .......................................................................... 4 1) Oxidative insertion ................................................................................................... 4 2) Halogen-metal exchange reactions .......................................................................... 7 3) Metalation reactions using amide bases ................................................................... 9 III. Objectives ..................................................................................................................... 12 Results & discussion ................................................................................................................ 14 I. Preparation of Polysubstituted Allenes via Regioselective Lateral Metalation of Benzylic Trimethylsilyl-Alkynes using TMPZnCl.LiCl ...................................................... 15 1) Introduction ............................................................................................................ 15 2) Preparation of trisubstituted allenes ....................................................................... 18 3) Preparation of tetrasubstituted allenes ................................................................... 21 II. New preparation of benzylic manganese chlorides by the direct insertion of magnesium into benzylic chlorides in the presence of MnCl 2·2LiCl ................................... 26 1) Introduction ............................................................................................................ 26 2) Preparation of benzylic manganese chlorides ........................................................ 28 3) Reaction of benzylic manganese chlorides with electrophiles .............................. 30 III. Transition metal free cross-coupling of aryl and N-heteroaryl cyanides with benzylic zinc reagents ......................................................................................................................... 33 1) Introduction ............................................................................................................ 33 2) Transition metal free benzylation of 4-cyanopyridines ......................................... 38 3) Transition metal free benzylation of polycyano-aromatics ................................... 44 IV. Sc(OTf) 3-catalyzed addition of bromomagnesium 2-vinyloxy ethoxide to various aldehydes leading to protected aldol products ...................................................................... 53 1) Introduction ............................................................................................................ 53 2) Preparation of the protected aldol products ........................................................... 57 V. Summary ...................................................................................................................... 64 1) Preparation of polysubstituted allenes via regioselective lateral metalation of benzylic trimethylsilyl-alkynes using TMPZnCl·LiCl ..................................................... 64 I TABLE OF CONTENTS 2) New preparation of benzylic manganese chlorides by the direct insertion of magnesium into benzylic chlorides in the presence of MnCl 2·2LiCl ............................... 65 3) Transition metal free cross-coupling of aryl and N-heteroaryl cyanides with benzylic zinc reagents ...................................................................................................... 66 4) Sc(OTf) 3-catalyzed addition of bromomagnesium 2-vinyloxy ethoxide to various aldehydes leading to protected aldol products ................................................................. 68 Experimental Section ............................................................................................................... 70 I. 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