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Dissertation - Rostocker Do · PDF fileErinreichung der Dissertation: 01 Oktober 2011 1. ... Ernst-Moritz-Arndt Universität Greifswald Rigorosum: 04. ... to Dr. Holger Feist for his

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Text of Dissertation - Rostocker Do · PDF fileErinreichung der Dissertation: 01 Oktober 2011 1. ......

  • Synthesis of Function

    Tetrahyd

    benzo[b]fluoren-

    b]pyrroles, Benz

    by Regioselect

    Domi

    Erla

    docto

    der Mathem

    Ghazwan Ali S

    nalized Benzofurans, Diaryl-Substitu

    dro-9,10-Anthracen-1-ones, 5,10-Diar

    -11-ones, Benzothieno[3,2-b]quinolin

    zofuro[3,2-b]quinolines, and Furo[3,

    tive Palladium(0)-Catalyzed Cross-C

    ino C-N Coupling/Annulation Reacti

    Dissertation zur

    angung des akademischen Grades

    or rerum naturalium (Dr. rer. nat.)

    matisch-Naturwissenschaftlichen Fakult

    der Universitt Rostock

    vorgelegt von

    alman geb. am 21. July 1979 Baghda

    Rostock, September 2011

    uted 1,2,3,4-

    ryl-11H-

    nes, Thieno[3,2-

    ,2-b]quinolines

    Coupling and

    ions

    tt

    ad, Iraq

    urn:nbn:de:gbv:28-diss2012-0018-7

  • Die vorliegende Arbeit entstand in der Zeit von April 2009 bis August 2011 am

    Institut fr Chemie der Universitt Rostock.

    Dekan: Prof. Dr. Christoph Schick, Mathematisch-Naturwissenschaftliche

    Fakultt, Universtt Rostock.

    Erinreichung der Dissertation: 01 Oktober 2011

    1. Gutachter: Prof. Dr. Dr. h.c. Peter Langer, Institut fr Chemie,

    Universitt Rostock

    2. Gutachter: Prof. Dr. Sabine Mller, Institut fr Bioorganic Chemie,

    Ernst-Moritz-Arndt Universitt Greifswald

    Rigorosum: 04. 01. 2012

    Prfer Hauptfach: Prof. Dr. Dr. h.c. Peter Langer

    (Institut fr Chemie, Universitt Rostock)

    Prfer Nebenfach: Prof. Dr. Reinhard Schrder

    (Institut fr Biowissenschaften, Universitt Rostock)

    Tag der Promotion: 31. 01. 2012

  • Wissenschaftliches Kolloquium: 2012

  • Affectionately Dedicated to My dearest Father and Mother

    for their exceptional love. Also, to my loving brothers and

    sisters for their cares and support.

  • ACKNOWLEDGEMENTS

    In the name of ALLAH, the beneficent, the merciful, who is Ubiquitous, Omniscient, worthy

    of all praise, without his blessings and help this work would never been accomplished.

    I feel great honor to express my utmost and sincere gratitude, appreciation, indebtedness to

    Prof. Dr. Peter Langer for giving me the apportunity to carry out my Ph.D. research in his

    research group and for providing efficient guidance and enerrgetic research environment

    during whole Ph.D. I always found him ready to facilitate my research problems by effective

    discussions, time devotion, unending trust and providing free hand in research.

    My deapest thanks, and gratitude are extended to the Deutscher Akademischer Austausch

    Dienst (DAAD) foundation for the generous financial support over three and a half past

    years.

    I wish to express my special gratitude to Dr. Martin Hein and Dr. Dirk Michalik for a number

    of nice and valuable talks about my research, to Dr. Holger Feist for his enthusiasm to teach

    about security instructions, to Dr. Alexander Villinger for their professional and accurate

    measuring X-ray crystallographic analysis of my compounds. I would also like to thank the

    members of NMR, IR, MS, and X-ray laboratories of the University of Rostock and the

    Leibniz Institute for Catalysis Rostock.

    I am thankful to all my past and present, foreigner and native colleagues of our research group

    for their support, research discussions, and for the friendly atmosphere they provided.

    Many thanks to my countryfellow and friends in Rostock (Dhafer Saber Zinad, Omer Akrawi,

    Nadi Eleya), for their enjoyable and meaningful company gave me not only support but also

    feeling like own country. I appreciate the support and help of Dr. Munawar Hussain during

    the early days of my Ph.D. here at Rostock.

    Finally I express my heartiest gratitude and respect to my mother and father, i have no words

    to acknowledge their contribution in my life, especially full support during the whole period

    of my life. I am fortunate enough to have such wonderful parents, without their constant

    encourgement, love and support it would have been impossible for me to finish my studies. I

    am also thankful to my dearest brothers and sisters who encouraged me through-out my

    studies and support me what and whenever they could.

    Ghazwan Ali Salman

    August 2011, Rostock,

    Germany

  • MAIN CONTENTS

    SUMMARY page 1

    CHAPTER 1 page 4 - 9

    Synthesis of Functionalized Benzofurans by Double Heck Reactions of 2,3-dibromo-5-(ethoxycarbonyl)furan and subsequent 6-Electrocyclization / Dehydrogenation

    The palladium(0)-catalyzed Heck cross-coupling reactions of 2,3-dibromo-5-(ethoxycarbonyl) furan provided functionalized 2,3-di(alkenyl)-5-(ethoxycarbonyl)furans by domino 'twofold Heck / 6 electrocyclization.The products were transformed to the corresponding functionalized benzofurans.

    CHAPTER 2 Page 10 - 18

    Regioselective Suzuki-Miyaura Reactions of the Bis(triflate) of 1,2,3,4-Tetrahydro-9,10-dihydroxyanthracen-1-one

    Suzuki-Miyaura cross coupling reactions of the

    bis(triflate) of 1,2,3,4 tetrahydro-9,10-

    dihydroxyanthracen-1-one was proceeded with different

    arylboronic acids to give mono- and diaryl 1,2,3,4-

    tetrahydro-9,10-dihydroxyanthracen-1-one. The reaction

    proceeded with very good site-selectivity in favour of

    position 10, due to electronic reasons.

  • CHAPTER 3 Page 19 - 25

    Site-selective Suzuki-Miyaura Reactions of the Bis(triflate) of 5,10-dihydroxy-11H-benzo[b]fluoren-11-one

    The Suzuki-Miyaura reaction of the bis(triflate) of 5,10-dihydroxy-11H-benzo[b]fluoren-11-one with aryl boronic acids gave 5,10-diaryl-11H-benzo[b]fluoren-11-ones. The reaction with one equivalent of arylboronic acids resulted in site-selective attack at the more hindered and more electronically deficient carbon atom at C-10 and two different aryl groups were prepared by sequential addition of two different aryl boronic acids.

    CHAPTER 4 Page 26 - 42

    Domino C-N coupling / annulation versus C-N coupling / hydroamination of 2-alkynyl-

    3-bromobenzothiophenes and 2-alkynyl-3-bromothiophenes. Highly efficient synthesis

    of benzothieno[3,2-b]quinolines and thieno[3,2-b]pyrroles

    While the palladium catalyzed

    reaction of 2-alkynyl-3-

    bromothiophenes with anilines

    afforded thienopyrroles by a domino

    C-N coupling / hydroamination

    process, the reaction of 2-alkynyl-3-

    bromobenzothiophenes with anilines

    resulted, under identical conditions, in

    the formation of

    benzothienoquinolines by a domino

    C-N coupling / annulation process.

    The electronic character of the aniline

    has an influence on the product

    distribution.

  • CHAPTER 5 Page 43 - 51

    Domino C-N Coupling / Annulation versus C-N Coupling / Hydroamination of 2-

    Alkynyl-3-bromobenzofurans and 2-Alkynyl-3-bromofurans. Highly Efficient Synthesis

    of Benzofuro[3,2-b]quinolines and Furo[3,2-b]quinolines The reaction of 2-alkynyl-3-

    bromofuran and 2-alkynyl-3-

    bromobenzofurans with electron rich

    anilines afforded Furo[3,2-

    b]quinolines and Benzofuro[3,2-

    b]quinolones, respectively by a

    domino C-N coupling / annulation

    process, but with anilines containing

    strong -acceptor substituents the

    both substrates afforded Furo[3,2-

    b]pyrrole and benzofuro[3,2-

    b]pyrroles, respectively by a domino

    C-N coupling / hydroamination

    process.

    EXPERIMENTAL SECTION Page 55 - 131

    APPENDIX Page 132

    ABBREVIATIONS Page 137

    REFERENCES Page 138

    ERKLRUNG Page 150

    LIST OF PUBLICATIONS Page 151

  • DETAILED CONTENTS

    1 Synthesis of Functionalized Benzofurans by Double Heck Reactions of 2,3-dibromo 5- (ethoxycarbonyl)furan and subsequent 6-Electrocyclization / Dehydrogenation 4

    1.1 General Introduction. 4

    1.2 Introduction . 6

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