Synthesis of functionalized 4-chlorophthalates, 2-naphthoates, 2-fluorobiaryls, and arylpyridines by cyclocondensation reactions of 1,3-bis(silyloxy)-1,3-butadienes and related dienes and by palladium(0) catalyzed cross coupling reactions [Elektronische Ressource] / vorgelegt von Obaid-ur-Rahman Abid

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• Publié par: universitat_rostock
• Publié le: 01 janvier 2010
• Nombre de lectures: 24
• Langue: English
• Poids de l'ouvrage: 3 Mo

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Synthesis of Functionalized 4-Chlorophthalates, 2-Naphthoates, 2-
Fluorobiaryls, and Arylpyridines by Cyclocondensation Reactions of 1,3-
Bis(silyloxy)-1,3-butadienes and Related Dienes and by Palladium(0)-
Catalyzed Cross-Coupling Reactions
DISSERTATION
zur
Erlangung des akademischen Grades
doctor rerum naturalium (Dr. rer. nat.)
der Mathematisch-Naturwissenschaftlichen Fakultät
der Universität Rostock
vorgelegt von
M.Phil Chemistry Obaid-ur-Rahman Abid geb. am 07.08.1977 in Rawalpindi
Aus Pakistan
Rostock, April 2010

urn:nbn:de:gbv:28-diss2010-0112-7
Dekan : Prof. Dr. Hendrik Schubert
1. Gutachter : Prof. Dr. Peter Langer, Institue of Chemistry, University of Rostock.
2. Gutachter : Prof. Dr. Torsten Linker, Institute of Chemistry, University of Potsdam.
Tag der Promotion : 06-07-2010












CONTENTS
Acknowledgements ……………………………………………………………………. vi
Abbreviations …………………………………………………………. vii
Summary …………………………………………………………. 1
Synthesis of Functionalized 4-Chlorophthalates, 2-Naphthoates,
2-Fluorobiaryls, and Arylpyridines by Cyclocondensation Reactions of 1,3-
Bis(silyloxy)-1,3-butadienes and Related Dienes and by Palladium(0)-
Catalyzed Cross-Coupling Reactions
1. Synthesis of highly functionalized biaryls by condensation
of 2-fluoro-1,3-bis(silyloxy)-1,3-dienes with 3-cyanochromones
and subsequent domino ′retro-Michael / aldol / fragmentation′
reactions ……………………………………………………………... 2
1.1 Introduction …………………………………………………. 2
1.2 Results and discussion ………………………………………. 2
1.3 Conclusion …………………………………………………… 7
2. Synthesis of 1,4-diaryl-2-naphthoates and 1,4-bis(alkynyl)-
2-naphthoates based on site-selective Suzuki-Miyaura and
Sonogoshira reactions ……………………………………………….. 9
2.1 General Introduction ………………………………………… 9
2.2 Introduction ………………………………………………….. 12
2.3 Results and discussion ……………………………………….. 13
2.4 Conclusion …………………………………………………… 22

3. Synthesis of 3,5-diaryl-4-chlorophthalates by [4+2] cycloaddition
of 1-ethoxy -2-chloro-1,3-bis(trimethylsilyloxy)-1,3-diene with
dimethyl acetylenedicarboxylate and subsequent site-selective
Suzuki-Miyaura reactions …………………………………………… 23
3.1 Introduction …………………………………………………. 23
3.2 Results and discussion ……………………………………….. 23
3.3 Conclusion …………………………………………………... 27
4. Synthesis of functionalized arylpyridines and arylpyrimidines
based on a Diels-Alder approach …………………………………... 29
4.1 Introduction …………………………………………………. 29
4.2 Results and discussion ………………………………………. 30
4.3 35

5. Abstract ……………………………………………………………… 36
6. Experimental Section ………………………………………………… 38
6.1 General: Equipment, chemicals and work technique ………………... 38
6.2 Procedures and spectroscopic data ………………………………….. 40
Referances …………………………………………………………… 97
Data for X-Ray Crystal Structures …………………………………… 105


ACKNOWLEDGEMENTS
By the grace of Allah, the Almighty, the creator of universe, who granted Hidayah to
the mankind and peace and blessings be upon his prophet, Hazrat Muhammad (Peace be
upon Him), who exhorted his followers to seek knowledge from cradle to grave, I've been
able to complete this academic enterprise.
It is my first and foremost obligation to express my sincere gratitude to Professor Dr.
Peter Langer my supervisor. His proper supervision, experience, time devotion and keen
interest enable me to accumulate this humble work. Some special words are due to my kind
supervisor in Pakistan Professor Dr. Nasim Hasan Rama, Department of Chemistry, Quaid-i-
Azam University, Islamabad for his great help and encouragement during my stay at Quaid-i-
Azam University.
I would like to acknowldge to Dr. Muhammad Sher and my friend Mr Farooq Ebad
for helpful discussions and friendship. I ought to submit my thanks to my dear friends, who
remembered me in their prayers and heart. I wish to acknowledge support and
encouragement provided by Olumide, Serge, Asad, Rasheed Khera, Sharif, Ihsan, Malik,
Nawaz, Hung, Tariq, Sajid, Naeem, Mukhtar Bhai, Yasin Bhai, Kamran Bhai and Munawar
Bhai.
I am thankful to all my past and present colleagues Zeeshan, Zeeshan Ahmad, Adeel,
Majid, Rasheed, Shkoor, Dhafer, Ghazwan, Mahal and Omer for their support
encouragement and help to pursue this work and all others whom I have missed here do
deserve equal credit.
Thanks also go to Dr. Martin Hein, Dr Holger Feist, Frau Jacob, Frau Anne Hallman
and Frau Claudia Vinke and all members of technical sections (NMR, IR, MS, EA and X-Ray
etc) of Rostock University.
Finally I express my heartiest gratitude and respect to my mother, father, dearest
brothers and sisters who encouraged me through-out my studies and supported me what and
whenever they could. Special thanks to Naeem Bhai for his continuous support in all fields of
life.
Obaid 27-04-2010
Abbreviations
Ar Aromatic
APT Attached Proton Test
ATCC American Type Culture Collection
nBuLi n-Butylithium
DEPT Distortionless Enhancement by Polarisation Transfer
EI Electronic Impact
ESI Electrospray Ionization
EtOAc Ethylacetate
HRMS High Resolution Mass Spectroscopy
IR Infrared Spectroscopy
LDA Lithium Diisopropylamide
MS Mass Spectrometry
Ph Phenyl
NEt Triethylamine 3
NMR Nuclear Magnetic Resonance
HMQC Heteronuclear Multiple Quantum Coherence
HMBC Heteronuclear Bond Correlation
COSY Correlated Spectroscopy
NOESY Nuclear Overhauser and Exchange Spectroscopy
MeSiOTf Trimethylsilyl-trifluoromethanesulfonate 3
MeSiCl Trimethylsilylchloride 3
mp. Melting Point
RCM Ring Closing Metathesis
TBAI Tetrabutyl Amonium Iodide
TBAF yl Fluoride
TFA Trifluoroacetic Acid
TfO Trifluoromethanesulfonic Anhydride 2
THF Tetrahydrofurane
TLC Thin Layer Chromatography
TMS Trimethylsilane
UV Ultraviolet Spectroscopy.