A new pathway for the total functionalization of the purine scaffold and for the preparation of new materials based on benzo[c][1,2,5]thiadiazole via Mg and Zn intermediates [Elektronische Ressource] / Silvia Daniela Zimdars

Silvia Daniela Zimdars

Informations

• Publié par: ludwig-maximilians-universitat_munchen
• Publié le: 01 janvier 2011
• Nombre de lectures: 27
• Langue: English
• Poids de l'ouvrage: 8 Mo

Extrait

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




A new Pathway for the Total Functionalization of the Purine
Scaffold and for the Preparation of new Materials Based on
Benzo[c][1,2,5]thiadiazole via Mg and Zn Intermediates







Silvia Daniela Zimdars

aus

Berlin








2011


Erklärung

Diese Dissertation wurde im Sinne von § 13 Abs. 3 bzw. 4 der Promotionsordnung vom
29. Januar 1998 (in der Fassung der vierten Änderungssatzung vom 26. November 2004) von
Herrn Prof. Dr. Paul Knochel betreut.



Ehrenwörtliche Versicherung

Diese Dissertation wurde selbständig, ohne unerlaubte Hilfe erarbeitet.





München, den 14.02.2011




…………………………………………
Silvia Daniela Zimdars





Dissertation eingereicht am: 01.03.2011
1. Gutachter: Prof. Dr. Paul Knochel
2. Gutachter: Prof. Dr. Heinz Langhals
Mündliche Prüfung am: 11.04.2011


















To Steffen and my family


This work was carried out from January 2007 to January 2011 under the guidance of Prof. Dr.
Paul Knochel at the Fakultät für Chemie und Pharmazie of the Ludwig-Maximilians-
Universität, Munich.

I would like to thank Prof. Dr. Paul Knochel for giving me the opportunity to prepare my PhD
thesis in his group, for the chance of working on this many-sided, interesting topic and for his
invaluable guidance throughout this time.
I am very grateful to Prof. Dr. Heinz Langhals for agreeing to act as a referee, as well as to
Prof. Dr. Thomas Bein, Prof. Dr. Manfred Heuschmann, Prof. Dr. Thomas Carell and Prof.
Dr. Hans Rudolf Pfaendler for the interest shown in this manuscript and their agreement to
take part in the examination.
I want to thank Klaus Groll, Cora Dunst and Veronika Werner for the careful correction of
this manuscript.
Thanks to all the past and present members who created a great working and party
atmosphere, particularly Andreas Wagner, Matthias Schade and Klaus Groll. I want to thank
especially Sebastian Bernhard, Dr. Fabian Piller, Thomas Kunz, Dr. Christian Rauhut, Dr.
Armin Stoll and Veronika Werner, for being the best lab mates one could imagine. I thank
Milica Jaric for her enormous help and great tea times, Cora Dunst and Tomke Bresser for
beeing part of the “Mittagspausencrew” and also Dr. Xaver Steemann for his friendship.
Thanks go to François Crestey, Xavier Mollat du Jourdin, Christelle Pecceu and Carina
Wiedemann for their contributions to this work. Moreover I thank my co-operation partners
Mirjam Dogru, Andreas Esterbauer, Andreas Sonnauer and Andreas Walter for the fruitful
colaborations.
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 for the tremendous support and to Steffen for his love and
encouragement throughout my studies and my PhD.


Parts of this Ph.D. Thesis have been published:

Heinz Langhals, Paul Knochel, Andreas Esterbauer, Andreas Walter, Silvia Zimdars
“Benzothiadiazoloperylene-amorphe funktionale Materialien“ Patent application DE 10
2009 048 848.0.

Silvia Zimdars, Xavier Mollat du Jourdin, François Crestey, Thomas Carell and Paul Knochel
“Trifunctionalization of the Purine Scaffold using Mg and Zn Organometallic
Intermediates” Org. Lett. 2011, 13, 792.

Silvia Zimdars, Heinz Langhals and Paul Knochel “Functionalization of the
Benzo[c][1,2,5]thiadiazole Scaffold via Mg-, Zn- and Mn-Intermediates“ Synthesis,
accepted for publication.




A. INTRODUCTION ..........................................................................................................1
1. Overview........................................................................................................................2
2. General preparation of functionalized organomagnesium and organozinc
intermediates.................................................................................................................3
2.1. Metal insertion into organic halides.........................................................................................3
2.1.1. Magnesium insertion.........................................................................................................3
2.1.2. Zinc insertion.....................................................................................................................5
2.2. Halogen/ magnesium exchange...............................................................................................6
2.3. Directed metalation with amide-bases ....................................................................................9
2.3.1. Directed metalation with magnesium amides ...............................................................9
2.3.2. Directed metalation with zinc amides..........................................................................11
3. Functionalization of heterocycles ............................................................................... 14
3.1. Functionalization of the purine scaffold...............................................................................15
3.2. Functionalization of the benzo[c][1,2,5]thiadiazole scaffold..............................................18
4. Objectives.................................................................................................................... 21
B. RESULTS AND DISCUSSION ....................................................................................23
1. Functionalization of the Purine scaffold.....................................................................24
1.1. Selection of the protection group..........................................................................................24
1.2. Successive deprotonation of purine derivatives at positions 8 and 6...............................26
1.3. Selection of the masked function at position 2 ...................................................................34
1.4. Full functionalization of the purine scaffold........................................................................36
2. Functionalization of the benzo[c][1,2,5]thiadiazole and the
benzo[c][1,2,5]oxadiazole scaffold..............................................................................45
2.1. Functionalization of the benzo[c][1,2,5]thiadiazole scaffold via Zn-, Mg- and Mn-
Intermediates ............................................................................................................................45
2.2. Synthesis of a new covalent organic framework..................................................................49
2.2.1. Introduction.....................................................................................................................49


2.2.2. Synthesis of 4,7-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)phenyl)benzo[c][1,2,5]thiadiazole as precursor for a COF....................................52
2.3. New benzo[c][1,2,5]thiadiazole and benzo[c][1,2,5]oxadiazole based perylene dyes ......54
2.3.1. Introduction.....................................................................................................................54
2.3.2. Preparation of precursors for new benzo[c][1,2,5]thiadiazole and
benzo[c][1,2,5]oxadiazole based perylene dyes............................................................54
3. Summary and Outlook ................................................................................................60
3.1. Functionalization of the purine scaffold...............................................................................60
3.2. Functionalization of the benzothiadiazole and benzofurazan scaffold............................61
C. EXPERIMENTAL SECTION......................................................................................64
1. General Considerations...............................................................................................65
2. Functionalization of the purine scaffold.....................................................................69
2.1. Synthesis of compounds 3-16 ................................................................................................69
2.2. Full functionalization of the purine scaffold......................................................................104
2.2.1. Typical procedures 1-5 .................................................................................................104
2.2.2. Synthesis of compounds 18a-24h...............................................................................106
3. Functionalization of the benzo[c][1,2,5]thiadiazole and benzo[c][1,2,5]oxadiazole
scaffold ..............................