Regioselective palladium(0)-catalyzed cross coupling reactions of brominated furans, thiophenes, pyrroles and selenophenes and synthesis of N,O-heterocycles by cyclocondensations of hydrazone and oxime dianions [Elektronische Ressource] / vorgelegt von Dang Than Tung
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Regioselective palladium(0)-catalyzed cross coupling reactions of brominated furans, thiophenes, pyrroles and selenophenes and synthesis of N,O-heterocycles by cyclocondensations of hydrazone and oxime dianions [Elektronische Ressource] / vorgelegt von Dang Than Tung

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UNIVERSITÄT ROSTOCK Regioselective Palladium(0)-Catalyzed Cross-Coupling Reactions of Brominated Furans, Thiophenes, Pyrroles and Selenophenes and Synthesis of N,O-Heterocycles by Cyclocondensations of Hydrazone and Oxime Dianions Dissertation zur Erlangung des Doktorgrades doctor rerum naturalium (Dr. rer. nat.) der Mathematisch-Naturwissenschaftlichen Fakultät der Universität Rostock vorgelegt von Dang Thanh Tung geb. am 28. Sep 1981 Hanoi, Vietnam. Rostock, February 2009 urn:nbn:de:gbv:28-diss2009-0095-8 Die vorliegende Arbeit entstand in der Zei von Mai 2006 bis November 2008 am Organische Chemie an der Universität Rostock. Erinreichung der Dissertation: 1. Gutachter: Prof. Dr. Peter Langer, Universität Rostock 2.rof. Dr. Thomas J.J. Müller, Universität Düsseldorf 3. Gutachter: Prof. Dr. Ernst Schaumann, Technische Universität Clausthal Tag der Abgabe: 25.02.2009 Rigorosum: 13.05.2009 Prüfungsvorsitzender: Prof. Dr. Martin Köckerling Prüfer Hauptfach: Prof. Dr. Peter Langer Prüfer Nebenfach: Dr.med.habil. Tiefenbach Birgit Wissenschaftliches Kolloquium: 26.05.2009 “Dedicated to my Parent and my uncle, Vu Van Chung”With my love and appreciation ! Who of you by worrying can add a single hour to his life?

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UNIVERSITÄT ROSTOCK



Regioselective Palladium(0)-Catalyzed Cross-Coupling Reactions
of Brominated Furans, Thiophenes, Pyrroles and Selenophenes
and Synthesis of N,O-Heterocycles by Cyclocondensations of
Hydrazone and Oxime Dianions




Dissertation

zur
Erlangung des Doktorgrades
doctor rerum naturalium (Dr. rer. nat.)
der Mathematisch-Naturwissenschaftlichen Fakultät
der Universität Rostock


vorgelegt von
Dang Thanh Tung geb. am 28. Sep 1981 Hanoi, Vietnam.

Rostock, February 2009

urn:nbn:de:gbv:28-diss2009-0095-8
Die vorliegende Arbeit entstand in der Zei von Mai 2006 bis November 2008
am Organische Chemie an der Universität Rostock.









Erinreichung der Dissertation:
1. Gutachter: Prof. Dr. Peter Langer, Universität Rostock
2.rof. Dr. Thomas J.J. Müller, Universität Düsseldorf
3. Gutachter: Prof. Dr. Ernst Schaumann, Technische Universität Clausthal


Tag der Abgabe: 25.02.2009

Rigorosum: 13.05.2009
Prüfungsvorsitzender: Prof. Dr. Martin Köckerling
Prüfer Hauptfach: Prof. Dr. Peter Langer
Prüfer Nebenfach: Dr.med.habil. Tiefenbach Birgit


Wissenschaftliches Kolloquium: 26.05.2009

























“Dedicated to my Parent and my uncle, Vu Van Chung”
With my love and appreciation !
Who of you by worrying can add a single hour to
his life?
Matthew 6:27
Acknowledgements
I thank all those who contributed to the success of this work and who
supported me during my time as a Ph.D. student.
Loi cam on
Fristly with my great respect, I would like to thank Prof. Dr. Peter
Langer, my supervisor, for providing me with the chemistry topic and
his readiness for discussion, help and encouragement. I am really lucky
to be his student. Without all his supports, the achievement of this work
would never be able to happen.
Danke
I wish to express my special gratitude to Dr. Martin Hein for not only
his interesting lecture in organic synthesis but also his help in
experimental guidance and discussion of chemistry, to Dr. Dirk
Michalik for several nice discussion and explanation as well as NMR,
13C, DEPT and other spectra, to Dr. Holger Feist for his enthusiasm to
teach about security instruction, to Dr. Alexander Villinger, Prof. Dr.
Helmut Reinke for their accurate measuring X-ray crytallographic Thank you
analyses. I would also like to thank the members of NMR, IR, UV,
MS, and X-ray laboratories of the University of Rostock and the
Leibniz Institute for Catalysis Rostock.
Graceful acknowledgements are made to Dr. Dang Thanh Tuan who is
always ready whenever I needed his help. Many thanks for his very
nice consideration, guidance and enthusiasm.
Cam on
I am thankful to all my past and present nice colleagues from many
countries Dr. Andreas Schmidt, Dr. Gerson Mross, Dr. Sven Rotzoll,
Dr. Stefanie Libnow, Dr. Ibrar Hussain, Dr. Mirza Arfan Yawer, Dr.
Rüdiger Dede, MSc. Vahuni Karapetyan, Dipl.-Biochem. Jörg-Peter
Gütlein, Dipl.-Chem. Alina Bunescu, Dipl.-Chem. Tam. T.H. Dang,
Peter Ehlers, Sebastian Reimann, Satenik Mkrtchyan ... , my friends
from JGEP, Rostock, K44B, 12A1 and all others whom I have missed
Vielen Dank
to mention here for uncounted discussions and their interest not only in
chemistry. They always encourage and help me to overcome the
obstacles in my Ph.D. life.
Many thanks to Dr. Dang Thanh Tuan, Dr. Farman Uhllah, Dr. Nasir
Rasool, MSc. Munawar Hussain, MSc. Rasheed Ahmad, MSc. Vahuni
Karapetyan, Satenik Mkrtchyan, Peter Ehlers for their contribution in
Thank a lot my research works.
The ju-jutsu and football people from Rostock I thank for their support
and an unforgettable time. To me they were and still are almost like
closefriends.
I could not forget to thank the leaders and staffs of Joint Graduate
Education Program (JGEP). Thanks to them, I could become a Ph.D. Danke schön
student at the University of Rostock. Financial support for my Ph.D.
Cam on
scholarship provided by the Vietnamese Misnistry of Education and
Training (MOET) is gratefully acknowledged.
Special thanks to all of my teachers who educated me in both life and
chemistry: Prof. Dr. Peter Langer, Prof. Dr. Hoang Trong Yem, Prof.
Dr. Ngo Thi Thuan, Prof. Dr. Tu Vong Nghi, Prof. Dr. Tran Thi Nhu
Many Thanks Mai and all others.
I would live to express my sincere thank you to my entire family for
their love and support. The meaning of their support and help in past
and present can hardly be expressed by words. The sentimental value
and spirit of family who not only always listens but also possesses a
whole lot of common sense -- cannot be underestimated. I love them
so, so … much.
I owe all of them in my life!

MAIN CONTENTS
SUMMARY Page 1-3
CHAPTER 1 Page 10 - 14
Synthesis of 2-(2-Arylethenyl)-5-arylfurans by Regioselective Palladium(0)-Catalyzed
Coupling Reactions of 2-(2-Bromo-2-nitroethenyl)-5-bromofuran
O O1 The Suzuki reaction of 2-(2-bromo-2-Br Ar
NO NO2 2
nitroethenyl)-5-bromofuran, readily
2
Br Ar available from furfural, resulted in
regioselective attack onto the furan moiety. This chapter was published in Synlett 2006, 17,
The alkenyl moiety could be functionalized 2812-2814 by Dang Thanh Tuan, Dang Thanh
in a second Suzuki reaction. Tung and Peter Langer*
Page 15 - 19CHAPTER 2
Regioselective Synthesis of Functionalized Pyrroles based on the first Palladium(0)-
Catalyzed Cross-Coupling Reactions of N-Methyltetrabromopyrrole
2 2Ar ArBr Br Regioselective Suzuki cross-coupling
reactions of 2,3,4,5-tetrabromo-1-
1 1Ar ArBr Br
N N methylpyrrole allow a convenient synthesis
Me Me of functionalized pyrroles.
This chapter was published in Tetrahedron Letter 2008, 49, 1698-1700 by Tung T. Dang,
Tuan T. Dang, Rasheed Ahmad, Helmut Reinke and Peter Langer*
CHAPTER 3 Page 20 - 27
Regioselective Sonogashira Reactions of N-Methyltetrabromo-pyrrole. First Synthesis of
Tri- and Tetra(1-alkynyl)pyrroles
N-Methyl-2,3,4,5-tetrabromopyrrole is
2 2R R transformed into a variety of alkylnyl-
Br Br substituted pyrroles by regioseletive
Sonogashira cross-coupling reactions. In
Br Br
1 1N N this context, the synthesis of the first tri-, R R
Me Me and tetra(1-alkylnyl)pyrrole is reported.
This chapter was accepted in Synlett 2009 by Farman Ulah, Tung T. Dang, Joachim

Heinicke, Alexander Villinger and Peter Langer*
I
Page 28 - 36CHAPTER 4
Efficient Synthesis of Substituted Selenophenes based on the First Palladium(0)-
Catalyzed Cross-Coupling Reactions of Tetrabromoselenophene
2 2R RBr Br Regioselective Suzuki cross-coupling
reactions of tetrabromoselenophene allow a
1 1R RBr Br Se convenient synthesis of aryl-substituted Se
selenophenes. High yields were obtained
using a novel biaryl monophosphine ligand. This chapter was published in Advanced
The first tetra(1-alkynyl)selenophene was Synthesis and Catalysis 2008, 350, 2109-2117
prepared in one step by a Sonogashira by Dang Thanh Tung, Alexander Villinger,
reaction of tetrabromoselenophene. and Peter Langer*
CHAPTER 5 Page 37 - 50
Regioselective Palladium(0)-Catalyzed Cross-Coupling Reactions and Metal-Halide
Exchange Reactions of Tetrabromothiophene
2 2R RBr Br The Suzuki reaction of tetrabromothiophene
with arylboronic acids provides a
1 1R RBr Br regioselective approach to various substituted SS
group thiophenes. During the optimization of
the conditions of each individual reaction, the
HO OH
solvent, the catalyst, the ligand and the
temperature played an important role.
Regioselective metal-halide-exchange
OO
reactions of tetrabromothiophene provide a HO C CO H2 2S S
convenient approach to various 2,5-OO
substituted 3,4-dibromothiophenes. 5-Alkyl-
2-trimethylsilyl-3,4-dibromothiophenes could
be prepared in a one-pot protocol by
This chapter was published in Tetrahedron sequential addition of trimethylchlorosilane
Letter 2007, 48, 845-847 and full papers was and alkyl bromides. The reaction of
submitted in Advanced Synthesis and tetrabromothiophene with methyl
Catalysis by Dang Thanh Tung, Dang chloroformiate and subsequent Suzuki
Thanh Tuan, Alexander Villinger, Haijun reactions afforded 3,4-diaryl-2,5-

Jiao, Christine Fischer and Peter Langer* bis(methoxycarbonyl)thiophenes. These
products were transformed into sulphur-
analogues of pyrrole natural products, such
as ningaline A.

II
Page 52 – 57CHAPTER 6
Synthesis of Pyrazole-3-carboxylates and Pyrazole-1,5-Dicarboxylates by One-Pot
Cyclization of Hydrazone Dianions with Diethyl Oxalate
O The one-pot cyclization of hydrazone
N
HN dianions with diethyl oxalate allows a
OEt
convenient synthesis of pyrazole-3-
1 2CO Et2 R RO carboxylates and pyrazole-1,5-
NH OEtN dicarboxylates.EtO+ CO Et2 2 OR1 OR N
N
OEt
1 2R R
This chapter was published in Tetrahedron Letter 2007, 48, 845-847 (>> highlighted in
Synfact 2007, 07, 0692) and Tetrahedron 2008, 64, 2207-2215 by Tung T. Dang, Tuan T.
Dang, Christine Fischer, Helmar Görls and Peter Langer*
Page 58 - 62CHAPTER 7
Regioselective Synthesis of 6-Halomethyl-5,6-dihydro-4H-1,2-oxazines based on
Cyclizations of Arylalkenyl-oximes
6-Iodo- and 6-bromomethyl-5,6-dihydro-4H-1,2-
I2OH O oxazines were prepared by condensation of
N N I
dilithiated acetophenone-oximes with +
Ar Br Ar
allylbromide and subsequent regioselective R R
iodine- or NBS-mediated cyclization.
This chapter was published in Tetrahedron 2008, 64, 8010-8015 by Vahuni Karapetyan,
Satenik Mkrtchyan, Tung T. Dang, Alexander Villinger, Helmut Reinke and Peter Langer*
EXPERIMENTAL SECTION Page 63 - 121
APPENDIX Page 124
ERKLÄRUNG Page 125
CURRICULUM VITAE Page 126
REFERENCE Page 130
III
DETAIL CONTENTS
P Part 1 1 Regioselective Palladium(0)-Catalyzed Coupling Reactions of
Bromosubstituted Furans, Thiophenes, Pyrroles, Selenophenes ............................. 4
1.1 Synthesis of 2-(2-Arylethenyl)-5-arylfurans by Regioselective Palladium(0)-
Catalyzed Coupling Reactions of 2-(2-Bromo-2-nitroethenyl)-5-bromofuran ...... 10
1.1.1 Introduction.......................................................................................................10
1.1.2 Results and Discussion......................................................................................11
1.1.3 Conclusion.........................................................................................................14
1.2 Regioselective Suzuki Cross-Coupling Reactions of 2,3,4,5-Tetrabromo-1-
methylpyrrole.......................................................................................................... 15
1.2.1 Introduction15
1.2.2 Results and Discussion16
1.2.3 Conclusion.........................................................................................................19
1.3 Regioselective Sonogashira Reactions of N-Methyl-Tetrabromopyrrole. First
Synthesis of Tri- and Tetra-(1-alkynyl)pyrroles..................................................... 20
1.3.1 Introduction20
1.3.2 Results and Discussion......................................................................................21
1.3.3 Conclusion.........................................................................................................27
1.4 Efficient Synthesis of Substituted Selenophenes based on the First Palladium(0)-
Catalyzed Cross-Coupling Reactions of Tetrabromoselenophene ......................... 28
1.4.1 Introduction.......................................................................................................28
1.4.2 Results and Discussion29
1.4.3 Conclusion.........................................................................................................36
1.5 Regioselective Palladium(0)-Catalyzed Cross-Coupling Reactions and Metal-
Halide Exchange Reactions of Tetrabromothiophene ............................................ 37
1.5.1 Introduction37
1.5.2 Results and Discussion......................................................................................38
1.5.3 Conclusion.........................................................................................................50
P Part 2 : Synthesis of N,O-Heterocycles based on Cyclocondensation Reactions of
Hydrazone and Oxime Dianions ............................................................................... 51
1.6 Synthesis of Pyrazole-3-carboxylates and Pyrazole-1,5-Dicarboxylates by One-Pot
Cyclization of Hydrazone Dianions with Diethyl Oxalate ..................................... 52
1.6.1 Introduction.......................................................................................................52
1.6.2 Results and Discussion53
1.6.3 Conclusion.........................................................................................................57
1.7 Regioselective Synthesis of 6-Halomethyl-5,6-dihydro-4H-1,2-oxazines based on
Cyclizations of Arylalkenyl-oximes ....................................................................... 58
1.7.1 Introduction58
1.7.2 Results and Discussion......................................................................................
1.7.3 Conclusion.........................................................................................................62
Experimental Section ............................................................................................................. 63
1.8 Material and Methods ............................................................................................. 63
1.8.1 General Remarks...............................................................................................63
1.8.2 Methods for Compound Characterization and Analysis ...................................
1.8.3 Chromatographic Methods................................................................................65
1.9 General Procedures.................................................................................................66
1.9.1 Synthesis of functionalized furans based on suzuki coupling reactions of 2-(2-
bromoethenyl)-5-furan ...................................................................................... 66
IV