Oxidative and transition-metal catalyzed cross-coupling reactions, preparation and coupling of S-heterocycles [Elektronische Ressource] / von Marcel Patrik Kienle

Marcel Kienle

Informations

• Publié par: ludwig-maximilians-universitat_munchen
• Publié le: 01 janvier 2010
• Nombre de lectures: 13
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

Dissertation zur Erlangung des Doktorgrades
der Fakultät für Chemie und Pharmazie
der Ludwig-Maximilians-Universität München







Oxidative and Transition-Metal Catalyzed Cross-Coupling
Reactions, Preparation and Coupling of S-Heterocycles






von

Marcel Patrik Kienle


aus Stuttgart







München 2010
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 und ohne unerlaubte Hilfe bearbeitet.


München, am 11.2.2010




__________________
Marcel Patrik Kienle



Dissertation eingereicht am 12.2.2010

1. Gutachter: Prof. Dr. Paul Knochel
2. Gutachter: Prof. Dr. Manfred Heuschmann

Mündliche Prüfung am 26. März 2010
This work was carried out from September 2006 to January 2010 under the guidance of Prof.
Dr. Paul Knochel at the Department Chemie und Pharmazie of the Ludwig-Maximilians-
Universität, Munich.



Firstly, 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 in the course of my
scientific research.

I am also very grateful to Prof. Dr. Manfred Heuschmann for agreeing to be my
“Zweigutachter”, as well as Prof. Dr. Herbert Mayr, Prof. Dr. Heinz Langhals, Prof. Dr. Ingo-
Peter Lorenz and Prof. Dr. Rudolf Knorr for their interest shown in this manuscript by
accepting to be referees.

I also would like to thank Andreas Wagner and Stefan Wunderlich 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 and
their help. Special thanks to my actual and former lab mates Giuliano Clososki, Srinivas
Reddy Dubbaka, Zhibing Dong, Nadège Boudet, Stefan Wunderlich, Cora Dunst, Andreas
Unsinn, Gabriel Monzon and especially Andreas Wagner.

I would like to thank Vicente del Amo, Srinivas Reddy Dubbaka and Cora Dunst for the
fruitful collaboration in the field of oxidative cross-coupling reactions and Stefan Wunderlich
and Andreas Unsinn for their valuable support in metalation reactions.

I thank Prof. Dr. Herbert Mayr and Prof. Dr. Heinz Langhals for the very stimulating
discussions.

I would also like to thank Vladimir Malakov, Simon Matthe, Beatrix Cammelade, 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.

I thank Florian Hinterholzinger, Steffi Seel, Klaus Groll, Marco Stein, Martin Olbrich and
Johanna Haidt for their contributions to this work in course of their “F-Praktika” and bachelor
thesis.

I would like to thank my parents for their great support, throughout my studies and my PhD.

Finally, I thank Sonja for her love and patient encouragement. Parts of this Ph.D. thesis have been published:

Communications and Full Papers:

1 “A Practical Synthetic Procedure for the Preparation of Tertiary Amines via the
Oxidative Coupling of Polyfunctional Aryl and Heteroaryl Amidocuprate”
M. Kienle, S. R. Dubbaka, V. del Amo, P. Knochel, Synthesis, 2007, 1272.

2 “Copper(I)-Mediated Oxidative Cross-Coupling Between Polyfunctional
Alkynyllithium and Arylmagnesium Reagents”
S. R. Dubbaka, M. Kienle, H. Mayr, P. Knochel, Angew. Chem. Int. Ed. 2007, 46,
9093.

3 “Directed Manganation of Functionalized Arenes and Heterocycles Using TMP Mn2
2MgCl 4LiCl” 2
S. H. Wunderlich, M. Kienle, P. Knochel, Angew. Chem. Int. Ed. 2009, 48, 7256.

4 “Oxidative Amination of Heteroaromatic Zinc Reagents Mediated by PhI(OAc) ” 2
M. Kienle, C. Dunst, P. Knochel, Org. Lett. 2009, 11, 5158.

5 “New Synthesis of Dibenzothiophenes and Related Classes of S-Heterocycles via an
Anionic Electrocyclization”
M. Kienle, A. Unsinn, P. Knochel, Angew. Chem. Int. Ed. manuscript accepted.

6 “iPrI-Acceleration of Negishi Cross-Coupling Reactions”
M. Kienle, P. Knochel, Org. Lett. manuscript submitted.

7 „Convenient Preparation of Transition Metal Organometallics via Directed
Metalation”
S. H. Wunderlich, M. Kienle, S. Matthe, P. Knochel, manuscript in preparation.

8 „Oxidative Amination Reaction of Zinc Organometallics Mediated by Cu(I) and
Oxidative Cycloamination for the Preparation of Annulated Indole Derivatives“
M. Kienle, A. J. Wagner, C. Dunst, P. Knochel, manuscript in preparation.

9 “Optically Active Biphenylene Bridged Periodic Mesoporous Organosilica in
Confined Environments”
Y. Li, A. Keilbach, S. Inagaki, M. Kienle, P. Knochel, T. Bein, manuscript in
preparation.

10 „Synthesis of Thiazole Oligomers and Their Potential Application in Blended Organic
Solar Cells”
M. Kienle, M. Hallermann, I. Kriegel, E. Da Como, P. Knochel, manuscript in
preparation.

11 „Preparation of Heterocyclic Amines via a Cu(I)-Mediated Oxidative Cross-Coupling
of Organozinc Reagents with Lithiumamides”
C. Dunst, M. Kienle, P. Knochel, manuscript in preparation.
Reviews:

1 “Modern Amination Reactions“
M. Kienle, S. R. Dubbaka, K. Brade, P. Knochel, Eur. J. Org. Chem. 2007, 4166.


























To Sonja and Isabel







Table of Contents

Table of Contents....................................................................................................................... 1
Abbreviations............................................................................................................................. 4
A Introduction ........................................................................................................................... 5
1. Amination Reactions ............................................................................................................. 6
1.1 Transition Metal Catalyzed Amination Reactions................................................................... 6
1.1.1 Palladium.............................................................................................................................................. 6
1.1.2 Nickel ................................................................................................................................................. 10
1.1.3 Copper ................................................................................................................................................ 11
1.2 Oxidative Amination Reaction................................................................................................. 12
2. Sonogashira Reactions........................................................................................................ 15
3. Negishi Cross-Coupling Reactions..................................................................................... 16
4. Preparation of Small Oligomers for the Application in Organic Solar Cells................... 17
5. Synthesis of Dibenzothiophenes and Related Classes of S-Heterocycles via an Anionic
Electrocyclization .................................................................................................................... 19
6. Objectives ............................................................................................................................. 21
B Results and Discussion........................................................................................................ 23
1. Oxidative Amination Using Organomagnesium Reagents................................................ 24
2. Oxidative Amination Using Organozinc Reagents ............................................................ 26
3. Copper(I)-Mediated Oxidative Coupling of Lithium Acetylides and Aryl Magnesium
Reagents in the Presence of Chloranil ................................................................................... 31
4. Oxidative Cross-Coupling Reactions Using Organomanganese Reagents....................... 38
5. iPrI-Accelerated Negishi Cross-Coupling Reactions......................................................... 43
6. Preparation of Small Oligomers for the Use as Donors in Blended Organic Solar Cells 51
6.1 Preparation of thiazole and thiophene-thiazole dimers......................................................... 51
6.2 Synthesis of trimers and tetramers.......................................................................................... 53
7. Synthesis of Dibenzothiophenes and Related Classes of S-Heterocycles via an Anionic
Electrocyclization .................................................................................................................... 58
8. Synthesis of Bis(trialkoxysilyl)biphenyls as Precursors for Periodi