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Synthetic Efforts Toward the Eastern Hemisphere of Theonellamide C Douglas D Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School 2013 Synthetic efforts toward the eastern hemisphere of theonellamide C Douglas D. Wong Louisiana State University and Agricultural and Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_dissertations Part of the Chemistry Commons Recommended Citation Wong, Douglas D., "Synthetic efforts toward the eastern hemisphere of theonellamide C" (2013). LSU Doctoral Dissertations. 210. https://digitalcommons.lsu.edu/gradschool_dissertations/210 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Doctoral Dissertations by an authorized graduate school editor of LSU Digital Commons. For more information, please [email protected]. SYNTHETIC EFFORTS TOWARD THE EASTERN HEMISPHERE OF THEONELLAMIDE C A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Douglas D. Wong B.S., Louisiana State University, 2003 December 2013 To My Family: To my mom and dad, Helena and Roger, who showed me that with hard work and dedication anything is possible. To my sister, Teresa, whose wisdom guides me. To my brother, Alex, whose example inspires me. To my sister, Lisa, whose honesty influences me. ii ACKNOWLEDGMENTS First and foremost, I would like to express my deepest gratitude for my advisor, Dr. Carol M. Taylor, for her years of guidance and support. Rarely will you find a person more passionate about her chemistry than Carol. I have learned from Carol that when you hold something in such high regard, you must work tirelessly in order to protect what is important. I am indebted to Carol for helping me strengthen my chemical intuition and professional foundation. I am also thankful for her “never too busy for her students” approach, more evidence that for Carol, it has and always will be about the chemistry. I honestly don’t know how I got to this point, but, I am grateful for every opportunity given to me. My appreciation goes to members of the Taylor research group, Benson, Ning, Saroj, Chamini and Chyree for scientific discussions, friendship and support. The past six years have not been easy but all of you have made this process exponentially better. I feel truly blessed to call each and every one of you friend. I also thank Molly of Dr. Waldrop group for explaining all things biology to an organic chemist. Special thanks to Alex of Dr. Vicente group for his friendship and encouragement. I would like to thank my committee members, Dr. William Crowe, Dr. Graca Vicente and Dr. Evgueni Nesterov for their advice and helpful suggestions. A heartfelt thanks to the late Dr. Dale Trelevean and Dr. Thomas Weldeghiorghis for their assistance in the acquisition and interpretation of more complex NMR spectra. I wish to thank Dr. Connie David for her help in all things related to mass spectrometry. I would be remiss if I did not thank the Department of Chemistry at LSU and the National Science Foundation for their financial support. iii TABLE OF CONTENTS ACKNOWLEDGMENTS ........................................................................................................................... iii LIST OF TABLES ...................................................................................................................................... vii LIST OF FIGURES ................................................................................................................................... viii LIST OF SCHEMES .................................................................................................................................... xi LIST OF ABBREVIATIONS AND SYMBOLS ....................................................................................... xv ABSTRACT ................................................................................................................................................ xx CHAPTER 1: THE THEONELLAMIDES (TNMs) AND RELATED COMPOUNDS ..................................................... 1 1.1 Isolation and Biological Activity ......................................................................................... 1 1.2 Structure Determination of Selected Amino Acids of TNM F6 ........................................... 6 1.3 The Relationship between Isotheopalauamide and Theopalauamide9 ............................... 10 1.4 Early Biological Studies .................................................................................................... 11 1.5 Synthetic Studies of TNM F by Shioiri and co-workers .................................................... 13 1.5.1 Synthesis of the Southern Hemisphere* of TNM F ............................................... 14 1.5.2 Synthesis of the Northern Hemisphere of TNM F ................................................. 15 1.6 Recent Biological Studies .................................................................................................. 16 1.7 Goals of the Current Work ................................................................................................. 23 1.8 References .......................................................................................................................... 24 CHAPTER 2: ASYMMETRIC SYNTHESIS OF ERYTHRO-β-HYDROXYASPARAGINE (EHYASN) ..................... 27 2.1 Proteinogenic vs Nonproteinogenic Amino Acids ............................................................. 27 2.2 Nonribosomal Peptide Synthesis ....................................................................................... 28 2.3 Identification and Occurrence of HyAsn in Nature ........................................................... 30 2.4 Previous Syntheses of 3-Hydroxyaspartic Acid ................................................................. 31 2.5 Previous Syntheses of β-Hydroxy-L-asparagine ................................................................ 33 2.5.1 Previous Syntheses of Erythro-β-Hydroxyasparagine ........................................... 33 2.5.2 Previous Syntheses of Threo-β-Hydroxyasparagine .............................................. 34 2.6 Retrosynthetic Analysis ..................................................................................................... 37 2.7 The Sharpless Asymmetric Aminohydroxylation .............................................................. 38 2.8 Synthesis of eHyAsn .......................................................................................................... 44 2.9 The eHyAsn-Phe Dipeptide ............................................................................................... 46 2.10 Experimental Section ......................................................................................................... 48 2.10.1 Experimental Procedures ..................................................................................... 49 2.10.2 Spectra .................................................................................................................. 55 2.11 References .......................................................................................................................... 71 CHAPTER 3: EARLY APPROACHES TO THE SYNTHESIS OF ABOA .................................................................... 75 3.1 Previous Synthesis of Aboa by Tohdo et al1 ...................................................................... 75 3.2 A Challenging Application of the Sharpless Aminohydroxylation Reaction .................... 77 3.3 The Regioreversed Sharpless Aminohydroxylation Reaction ........................................... 79 iv 3.4 Attempted Synthesis of Triene 175, an Aboa Precursor .................................................... 81 3.5 A Model System for the Regioreversed SAH .................................................................... 84 3.6 The Nitroaldol Reaction ..................................................................................................... 85 3.7 Wolf’s Asymmetric Nitroaldol Reaction ........................................................................... 87 3.8 The Second Approach for the Synthesis of Aboa: Application of Wolf’s Nitroaldol Reaction ............................................................................................................ 89 3.9 A Model System for Wolf’s Nitroaldol Reaction .............................................................. 89 3.10 Experimental Section ......................................................................................................... 92 3.10.1 Experimental Procedures ..................................................................................... 92 3.10.2 Spectra ................................................................................................................ 103 3.11 References ........................................................................................................................ 125 CHAPTER 4: RECENT APPROACHES TO THE SYNTHESIS OF APOA AND ABOA ........................................... 129 4.1 The Third Approach to the Synthesis of Aboa and Apoa ................................................ 129 4.2 Preparation of the Phosphonate Ester Fragments for Aboa and Apoa Synthesis............. 130 4.3 Preparation of the Aldehyde Fragment for Aboa and Apoa Synthesis
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