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Your Name Here THE DESIGN, DEVELOPMENT AND SYNTHESIS OF SECONDARY BINDING ELEMENTS FOR THE CONSTRUCTION OF POLYAZAMACROCYCLIC INOSITOL PHOSPHATE RECEPTORS FOR USE AS BIOLOGICAL PROBES OF PHOSPHATIDYLINOSITOL METABOLISM AND THERAPEUTIC AGENTS FOR THE TREATMENT OF BIPOLAR DISORDER by ANTHONY WAYNE WARREN (Under the Direction of Thomas E. Johnson) ABSTRACT Significant progress has been made in the design, development and synthesis of compounds able to provide secondary binding elements in the construction of a new class of polyazamacrocyclic inositol phosphate receptors. The secondary binding elements explored were based on a myo-inositol core structure, and were functionalized at the C1 and C4 positions with ether linked extended masked aldehyde groups as cyclization handles. Installation of the extended aldehyde on the inositol ring system was accomp- lished using the Williamson method for ether synthesis and provided consistent yields of about 80% across the gamut of latent aldehydes tested. Several molecules bearing differ- entially protected aldehyde moieties, for the purpose of regioselective macrocyclization into a compound designed to host Ins(1,4)P2 molecules, were synthesized. The three specific molecules holding the most promise for future efforts in this area were (±)1,4-O- Bis(2-[1,3]Dioxanylethoxy)-2,3:5,6-Di-O-cyclohexylidene-myo-inositol, (±)1,4-Di-O- allyl-2,3:5,6-Di-O-cyclohexylidene-myo-inositol and (±)1,4-Di-O-propargyl-2,3:5,6-Di- O-cyclohexylidene-myo-inositol. The latent aldehyde alkynyl function present in the last compound was successfully unmasked via hydroboration-oxidation chemistry and was readily isolated as a near crystalline compound, following size exclusion chromatography using SX-8 mesh BioBeads. INDEX WORDS: polyazamacrocycles, phosphatidylinositol metabolism, myo- inositol, host-guest chemistry, second messengers, bipolar disorder, lithium treatment, manic depression, phospholipids, phosphatidylinositol cycle, G-protein coupled receptors, receptor- ligand complexes, signal transduction, inositol phosphate receptors, anion receptors, molecular recognition THE DESIGN, DEVELOPMENT AND SYNTHESIS OF SECONDARY BINDING ELEMENTS FOR THE CONSTRUCTION OF POLYAZAMACROCYCLIC INOSITOL PHOSPHATE RECEPTORS FOR USE AS BIOLOGICAL PROBES OF PHOSPHATIDYLINOSITOL METABOLISM AND THERAPEUTIC AGENTS FOR THE TREATMENT OF BIPOLAR DISORDER by ANTHONY WAYNE WARREN Bachelor of Science, East Tennessee State University, 1996 A Dissertation Submitted to the Graduate Faculty of The University of Georgia in Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY ATHENS, GEORGIA 2003 © 2003 Anthony Wayne Warren All Rights Reserved THE DESIGN, DEVELOPMENT AND SYNTHESIS OF SECONDARY BINDING ELEMENTS FOR THE CONSTRUCTION OF POLYAZAMACROCYCLIC INOSITOL PHOSPHATE RECEPTORS FOR USE AS BIOLOGICAL PROBES OF PHOSPHATIDYLINOSITOL METABOLISM AND THERAPEUTIC AGENTS FOR THE TREATMENT OF BIPOLAR DISORDER by ANTHONY WAYNE WARREN Major Professor: Thomas E. Johnson Committee: Robert S. Phillips Philip J. Bowen Electronic Version Approved: Maureen Grasso Dean of the Graduate School The University of Georgia August 2003 DEDICATION I owe this work, and any opportunities that may come from it, to the one person who has never faltered in her belief in me—my wife Maria. Nine years ago, she rescued me from what I believed to be a lifelong date with an uncertain destiny in exchange for a lifelong love affair with the woman of my dreams. Her love and commitment to me, and our marriage, transformed my existence and breathed new life into a tired soul. Her confidence in me grew stronger as the years ensued and she provided a bedrock solid support system to counter my manic tendencies. This milestone of achievement in my life could not have been reached without her constant compassion, understanding and commitment to my efforts, both physically and emotionally. She has unselfishly taken on the care of both myself, and our beautiful daughter Hannah, during these past five months while I’ve been chained to this laptop and locked away in my office. I am also grateful to all the time she has managed to find during this hectic period to help me with the spectra found throughout this work. Thank you so much Maria, I love you with all my heart. I must also dedicate part of this work to my daughter, Hannah Jade, for her patience and understanding as she has been somewhat fatherless over the past few months while daddy “conshentwates” and makes late night runs to “chemistreet.” Thank you also for the rocks, Buga, I’ll cherish them like Zuzu’s petals. Finally, I dedicate an equal portion of this manuscript to my parents Peggy and Alonzo Warren for their many many years of tireless emotional and financial support, even when it seemed certain to me that I’d never make it—they always knew better. iv ACKNOWLEDGEMENTS I’d like to thank Dr. Thomas Johnson for all his guidance throughout my tenure as a graduate student in his labs. His optimistic outlook never wavered, and we were quite the dichotomy much of the time as we frequently acted to counter one another’s often extreme polarities when it came to gauging the progress of a particular endeavor. I’d be hard pressed to name a more congenial mentor from the several I’ve had over the years in both industry and academia. His optimism and nearly to-a-fault patience made working under his guidance truly enjoyable, and he was always able to impress me with his broad knowledge, and genuine liking for the field of chemistry and its outstanding practitioners. Dr. Robert Phillips simply knows everything about everything and it’s scary to think just how much more he probably used to know. Like Detective Robert Goran on Law and Order: Criminal Intent, his insight always provided just the right amount of enlightenment to push you further into the dark. I’d also like to acknowledge the fact that Dr. Philip Bowen has contributed extensively to my understanding of reaction mechanics through his lectures on stereochemistry and his computational vantage point on synthetic organic chemistry. As for the group members in my past, my strongest acknowledgement obviously goes to Andrew Pearson, with whom I shared a lab and friendship for more than five years. He taught me too much about computers, was a great sounding board, and kept the lab a fun place to work. Thanks also to Brad, Shili, Pallavi, Angil, Walter and even Billy. And then there’s George…oh, look! I’m out of space! Thanks George, really. v TABLE OF CONTENTS Page ACKNOWLEDGEMENTS.................................................................................................v CHAPTER 1 LIGAND-RECEPTOR MEDIATED SIGNAL TRANSDUCTION: A HISTORICAL PERSPECTIVE OF CELLULAR COMMUNICATION ....1 1.1 Life, Communication and Cellular Signaling.........................................1 1.2 First Messengers in Ligand-Receptor Mediated Signal Transduction: Hormones, Neurotransmitters, and Local Mediators......3 1.3 Second Messengers in Ligand- Receptor Mediated Signal Transduction ................................................6 1.4 The Phosphatidylinositol Response and Inositol Triphosphate as a Second Messenger .......................................9 1.5 Ion Channels, Tyrosine Kinases, and G-Protein Linked Receptor Types in Ligand-Receptor Mediated Signal Transduction ...12 1.6 Guanosine Triphosphate-Protein Linked Receptors in Ligand-Receptor Mediated Signal Transduction .............................17 1.7 References ............................................................................................20 2 EXPLORATION OF THE PHOSPHATIDYLINOSITOL CYCLE: THE NEED FOR MORE INVESTIGATIVE TOOLS ........................................23 2.1 Introduction ..........................................................................................23 2.2 The Phosphatidyl Inositol Cycle and a Multitude of Inositol Phosphates................................................23 2.3 Inositol Phosphates, a Multitude of Second Messengers?...................26 vi 2.4 Efforts Toward Assigning Second Messenger Roles to Inositol Phosphates ..............................................27 2.5 The Inositol Phosphate Receptor Research Project..............................31 2.6 References ............................................................................................33 3 A REVIEW OF THE CURRENT LITERATURE ON SYNTHETIC NITROGEN CONTAINING ANION RECEPTORS AND INOSITOL PHOSPHATE BOUND HOST-GUEST COMPLEXES ............................35 3.1 Host-Guest Chemistry, a Brief History................................................35 3.2 Design Aspects Important For Molecular Recognition........................41 3.3 Nitrogen Centric Anion Binding Motifs in Abiotic Receptors ...........49 3.4 Abiotic Inositol Phosphate Receptors ................................................128 3.5 Conclusion..........................................................................................137 3.6 References ..........................................................................................139 4 THE DESIGN AND SYNTHESIS OF ABIOTIC HOSTS FOR INOSITOL POLYPHOSPHATE GUEST MOLECULES I ........................................154 4.1 Introduction ........................................................................................154 4.2 The Physiochemical Nature of Inositol Phosphates...........................155 4.3 Design Aspects of Inositol Phosphate Receptors...............................162 4.4 Design and Synthesis Strategies For Azacyclophane Inositol Phosphate Receptors...........................................................................169
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