Synthesis of homophthalates, 2-(arylsulfonyl)pyridines, 6-(thien-2-yl)salicylates, dibenzo[b,d]pyran-6-ones, trifluoromethyl- and fluoro-substituted biaryls by [4+2] and [3+3] cyclizations of 1,3-bis(silyloxy)-1,3-butadienes [Elektronische Ressource] / vorgelegt von Ibrar Hussain

Description

Synthesis of Homophthalates, 2-(Arylsulfonyl)pyridines, 6-(Thien-2-yl)salicylates, Dibenzo[b,d]pyran-6-ones,Trifluoromethyl- and Fluoro-Substituted Biaryls by[4+2] and [3+3] Cyclizations of 1,3-Bis(silyloxy)-1,3-butadienes urn:nbn:de:gbv:28-diss2008-0072-2I n a u g u r a l d i s s e r t a t i o n zurErlangung des akademischen Grades doctor rerum naturalium (Dr. rer. nat.) an der Mathematisch-Naturwissenschaftlichen Fakultät derUniversität Rostock vorgelegt von Ibrar Hussain geboren am 10-05-1979 in Attock, Pakistan Rostock, 30-04-2008 iDekan : 1. Gutachter : 2. Gutachter : Tag der Promotion : ii Affectionately Dedicated to “My parents (Late), Brothers and Sisters” iiiCONTENTS Acknowledgements AbbreviationsGeneral Introduction 1 Summary 3 Synthesis of Homophthalates, 2-(Arylsulfonyl)pyridines,6-(Thien-2-yl)salicylates,Dibenzo[b,d]pyran-6-ones, Trifluoromethyl- and Fluoro-Substituted Biaryls by [4+2] and [3+3] Cyclizations of 1,3-Bis(silyloxy)-1,3-butadienes1. One-Pot Synthesis of Salicylates based on Regioselective [3+3] Cyclizations of1,3-Bis(trimethylsilyloxy)-1,3-butadienes and comparison of Regioselectivities 5 1.1. Synthesis of 1,3-bis(trimethylsilyloxy)buta-1,3-dienes 5 1.1.1. Introduction 5 1.1.2. Results and discussion 7 1.1.3. Conclusions 12 1.2. Synthesis of 2,4-Bis(trimethylsilyloxy)-1,3-pentadiene 13 1.2.1. Introduction 10 1.2.2.

Informations

• Publié par: universitat_rostock
• Publié le: 01 janvier 2008
• Nombre de lectures: 53
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

idines, -(Arylsulfonyl)pyrSynthesis of Homophthalates, 2

6-(Thien-2-yl)salicylates, Dibenzo[b,d]pyran-6-ones,

Trifluoromethyl- and Fluoro-Substituted Biaryls by

nes ations of 1,3-Bis(silyloxy)-1,3-butadie[4+2] and [3+3] Cycliz

urn:nbn:de:gbv:28-diss2008-0072-2

I n a u g u r a l d i s s e r t a t i o n

zur

ischen Grades Erlangung des akadem

m (Dr. rer. nm naturaliudoctor rerut.) a

akultät schaftlichen Fatisch-Naturwisseneman der Math

der

Universität Rostock

vorgelegt von

Ibrar Hussain

10-05-1979 geboren am

kistan ain Attock, P

Rostock, 30-04-2008

i

Dekan :

: Gutachter 1.

2. : Gutachter

: Promotion der Tag

ii

Affectionately Dedicated to

“My parents (Late), Brothers and Sisters”

iii

ents AcknowledgemAbbreviations

1 Introduction General Summary 3

CONTENTS

rylsulfonyl)pyridines,6-(Thien-2-yl)salicylates,Synthesis of Homophthalates, 2-(A

Dibenzo[b,d]pyran-6-ones, Trifluoromethyl- and Fluoro-Substituted Biaryls by

xy)-1,3-butadienes[4+2] and [3+3] Cyclizations of 1,3-Bis(silylo

One-Pot Synthesis of Salicylates based on Regioselective [3+3] Cyclizations of1. 5 ethylsilyloxy)-1,3-butadienes and comparison of Regioselectivities 1,3-Bis(trim1.1. Synthesis of 1,3-bis(trimethylsilyloxy)buta-1,3-dienes 5

Introduction 1.1.1. 5

7 discussion and Results 1.1.2. 12 Conclusions 1.1.3.

1.2. Synthesis of 2,4-Bis(trimethylsilyloxy)-1,3-pentadiene 13

10 Introduction 1.2.1.

1.2.2. 11 discussion and Results 12 Conclusions 1.2.3. One-Pot Synthesis of 6-(Thien-2-yl)salicylates based on Regioselective [3+3] 1.3. Cyclizations of 1,3-Bis(trimethyl-silyloxy)-1,3-butadienes 13
13 Introduction 1.3.1.

13 discussion and Results 1.3.2. 19 Conclusions 1.3.3.

ethyl)-salicylates by 4-Aryl- and 4-Hetaryl-6-(trifluoromSynthesis of1.4. Regioselective Cyclization of 1,3-Bis-(silyloxy)-1,3-butadienes with1.4.1. Introduction 1-Aryl-1-silyloxy-3-(trifluorom 19 ethyl)prop-1-en-3-ones 19

20 discussion and Results 1.4.2.

25 Conclusions 1.4.3.

2. ]pyran-6-ones based on a [3+3] Cyclization b,d Biaryls and Dibenzo[Synthesis ofStrategy 26
26 Introduction 2.1.

iv

28 discussion and Results 2.2. 31 Conclusions 2.3.

3. Regioselective Synthesis of Fluorinated Biaryls, 6H-Benzo[c]chromen-6-ones
al [3+3] Cyclizations ofand Fluorenones based on Form 32 Ethers) Enol 1,3-Bis(Silyl 3.1. Synthesis of Fluorinated Biaryls 32
32 Introduction 3.1.1. 33 discussion and Results 3.1.2. 38 Conclusions 3.1.3. 38 Lactones Fluorinated 3.2. 38 Introduction 3.2.1. 39 discussion and Results 3.2.2. 40 Conclusions 3.2.3. 40 Fluorenones 3.3. 40 Introduction 3.3.1. 41 discussion and Results 3.3.2. 43 Conclusions 3.3.3.

4. 4.1. 4.2. 4.3.

5.

5.1. 5.2. 5.3.

.6

39

41

4-Hydroxy- and 2,4-Dihydroxy-homophthalates by [4+2]Synthesis ofethylsilyloxy)-1,3-butadienesCycloaddition of 1,3-Bis(trim 44 Allene-1,3-dicarboxylate ethyl Dimwith 44 Introduction discussion and Results 46 51 Conclusions

ydroxypyridines by Functionalized 2-(Arylsulfonyl)-4-hSynthesis ofethylsilyloxy)-1,3-butadienes Heter-Diels-Alder Reaction of 1,3-Bis(trim 52 Cyanides Arylsulfonyl with 52 Introduction 53 discussion and Results 57 Conclusions

Abstract 5

53

v

8

7.

7.1.

7.2.

Section ental Experim

60

ent, chemGeneral: Equipmicals and work technique

data spectroscopic and Procedures

References

130

Data for X-Ray Crystal Structures

CurriculumVitae

Declaration

155

158

61

140

vi

60

ACKNOWLEDGEMENTS

rthy of all praise and oniscient, Who is Ubiquitous, OmIn the name of Allah, Wo guides in darkness and helps in difficulties. I do obeisance in thanks hCreator of all of us, Wand gratitude for all His blessings, due to which I was able to accomplish this strenuous task.
), for oly prophet Hazrat Muhammad (Peace be upon HimAll respect for the Hghty Allah and also for imenlightening our conscious with the essence of faith in Alprophesying the code of life (The Holy Quran). ated without the keen The work presented in this dissertation would never be consumminterest, proficient suggestions, guidance, and persistent encouragement of my research
supervisor, Prof. Dr. Peter Langer., without all these favors from him, accomplishment of this
ely difficult. work would have been extremMy sincere appreciations are extended to my friend Mirza A. Yawer for providing
the pany during this period. I do acknowledge the financial support from an enjoyable comema Naurin for her Higher education commission of Pakistan for scholarship and Mrs. Saim friend Irfan who always encouraged yank to must thconstant help through out the tenure. I mme whenever I was disappointed. I am thankful to all my lab fellows Ahmad mahal, Majid
pany. r their support and nice comoide Fatunsin fRiahi, Mohanad Shkoor and Olumm I am really thankful to Dr. Tuan Thanh Dang and Dr. Phoung Thi Bich Nguyen, whohelped me a lot whenever I needed them. This acknowledement can’t be completed without
thanking to all mAbid, Sven, Satti, Renskembe, Inam, Adeel, and Rasers of our research group and friends, Nasir, Sher, Tung, Jope, Gerson, hid. I also acknowledge the nice company of
I would say thanks to Dr. Martin Hein for Mukhtar while spending the free time in rostock.his scientific help and all members of technical sections (NMR, IR and Mass spectrometry) of
er Alexander Villinge for Prof. Helmut Reinke,Universitiy of Rostock. Thanks are also duar Görl (University of Jena) for X-ray crystallography. (University of Rostock) and Dr. Helmst important is, to say that I have a great debt on my life due to the enormous oThe mShah for their divine love, and Mrs. S.S.H. parents, brothers, sisters, Mr.ysacrifices of ment and continuous support throughout my studies. prayers, constant care, encouragemWhatever, I am, that is because of the countless prayers of my parents, who instilled in me, a
for education and the value of being organized.charm

vii

Ibrar Hussain

AromAr Attached APT Am ATCC BuLi n Distortionless DEPT Electronic EI ElectrosprayESI Ethylacetate EtOAc HRMS Infrared IR Lithium LDA Mass MS Phenyl Ph Triethy NEt3 NMR HMQC Heteronuclear HMBC Correlated COSY NOESY SiOTf Me3 SiCl Me3 Melting mp. Ring RCM Tetrabutyl TBAI Trifluoroacetic TFA Trifluorom O Tf2 Tetrahydrofurane THF Thin TLC Trim TMS UV

ns Abbreviatio

atic Test Proton Collection Culture Type erican -ButylithiumnEnhancement by Polarisation Transfer
Ionization Ionization

High Resolution Mass Spectroscopy spectroscopy ide diisopropylam etry Spectrom

ine lamNuclear Magnetic Resolution Coherence QuantumMultiple Heteronuclear Bond Multiple Correlation pectroscopy SOverhauser and Exchange Spectroscopy Nuclear thanesulfonate eethylsilyl-trifluoro mTrimride ethylsilylchloTrimpoint Metathesis Closing iodie amoniumacid anhydride ethanesulfonic

atography ChromLayer ethylsilane y iolet SpectroscopUltrav

viii

General introduction of the inghas unique place in our pattern of understandistry Like all sciences, chemething more. It sitry is somolecules. But the organic chem It is the science of muniverse.lecules of nature both ody the mit grows. Of course we need to stuliterally creates itself as because they are interesting in their own right and because their functions are important to our
daily lives. Organic chemistry often studies the life by making new moleculs that give
lecules actually present in living things. Natural o the mation not available frominforment of new portant role in discovery and developm improducts continue to play anpharmaceuticals, as clinically useful drugs, as starting materials to produce synthetic drugs, or
as lead structures from which a synthetic drug can be designed.1 Menthol is the famous
example of flavouring compound extracted from the essential oil of spearmint. At the same
portant role l products play an increasingly impounds not related to naturae, synthetic comtimthodology have provided a eents in synthetic mfor drug discovery. Continuous improvemstances. ray of synthetic subt access to a vast arconvenienent of new ad structures for the developmNatural products often represent important le2antibber of natural products exhibit antibiotic activity. Since the In fact, a numiotics. scores of e number of antibiotics has been isolated fromdiscovery of penicillin, a largmicroorganisms.3 The discovery of new important anti-infective compounds includes both
sinin, a sesquiterpene with endoperoxide imal sources. For example, asteplant and animmoiety, was isolated from Astemisia annua, a Chinese medicinal plant, which has been used
ent of new drugs includes ria. The developmalaent of min China for centuries for treatmsynthetic and semi-synthetic studies, microbial transformations, the biological screening and
of a