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Cation Clock Reactions for the Determination of Relative Reaction Kinetics in Glycosylation Reactions

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Cation Clock Reactions for the Determination of Relative Reaction Kinetics in Glycosylation Reactions Wayne State University Wayne State University Dissertations 1-1-2018 Cation Clock Reactions For The etD ermination Of Relative Reaction Kinetics In Glycosylation Reactions Philip Adero Wayne State University, Follow this and additional works at: https://digitalcommons.wayne.edu/oa_dissertations Part of the Organic Chemistry Commons Recommended Citation Adero, Philip, "Cation Clock Reactions For The eD termination Of Relative Reaction Kinetics In Glycosylation Reactions" (2018). Wayne State University Dissertations. 2086. https://digitalcommons.wayne.edu/oa_dissertations/2086 This Open Access Dissertation is brought to you for free and open access by DigitalCommons@WayneState. It has been accepted for inclusion in Wayne State University Dissertations by an authorized administrator of DigitalCommons@WayneState. CATION CLOCK REACTIONS FOR THE DETERMINATION OF RELATIVE REACTION KINETICS IN GLYCOSYLATION REACTIONS by PHILIP OUMA ADERO DISSERTATION Submitted to the Graduate School of Wayne State University, Detroit, Michigan in the partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY 2018 MAJOR: CHEMISTRY (Organic) Approved By: __________________________________________ Advisor Date __________________________________________ __________________________________________ __________________________________________ __________________________________________ DEDICATION This dissertation is dedicated to God for his providence and mercy, and to my family for the unconditional love and support ii ACKNOWLEDGMENTS I would like to express my profound gratitude to my graduate adviser, Professor David Crich for his guidance and encouragement throughout my research work in his laboratory at Wayne State University. I thank him for the confidence he had in me, for his constant unwavering support for my academic excellence and for inspiration and mentorship throughout my Ph.D studies. I wish to thank my committee members comprising; Prof. Jennifer Stockdill, Prof. Sarah Trimpin and prof. Jianlong Zhu for contributing their time, energy and suggestions to this dissertation and defense. I would like to thank my previous advisor, Prof. Peter Norris for his immense work in shaping my career by encouraging me to pursue Ph.D studies at Wayne State University. This has totally transformed my scientific knowledge. I would like to give great gratitude to my past and present labmates. First, to the postdoc in our: Dr. Takayuki Furukawa, for the collaborative work, Dr. Takayuki Kato, Dr. Takahiko Matzushita. Dr. Szyman Buda, Dr. Suresh Dharuman, Dr. Oskar Popik, Dr. Parasuraman, Dr. Vikram Sarpe and Dr. Govind. They had great laboratory techniques. Many thanks to my batchmates, Dr. Amr Sonusi, Dr. Peng Wen, Dr. Girish Sati, and Dr. Harsha Amarasekhara. Without their encouragement and support I would not have been be able to finish this Ph.D. I would like to thank my labmates: Sandeep Dhanju, Bibek Dhakal, Guanyu Yang, Michael Pirrone, Jonny Quirke, Dean Jarios, Tim Mcmillan, Philemon Ngoje, Mohammad Hawsawi, Nuwan Kondasinghe, Sameera Jayanath, Onobun Emmanuel, Fathima Rukshana, Kondor Courtney and Samarbakhsh Amirreza. They are amazing and very responsible people who constantly maintained the operations of the Crich lab. I feel short of words to express a deep sense of respect and gratitude iii for my friend and benchmate Dr. Amr Sonusi. In all my difficult moments, I always found him on my side to guide me in every way possible.we not only shared a good rapport with him but also find his criticism and suggestion fruitful in my graduate career. My special thanks are due to my siblings; Nicholas Adero, Rose Akinyi and Hellen Adhiambo for their unconditional support since the death of my parents. They saw me through my life after the death of my parents and endless encouragement. I always found them standing by my side through thick and thin. I owe more gratitude than I can express to my cousin Dr. James Onyona and for their financial support. I feel short of words to express a deep sense of respect and gratitude for my friend and senior Erick Amuka. My special thanks to my beloved wife Dinah Akinyi for her unconditional love and support in the last five years, I am deeply indebted to her for their unwavering faith in me. iv TABLE OF CONTENTS Dedication ....................................................................................................................................... ii Acknowledgments.......................................................................................................................... iii Table of Contents ............................................................................................................................ v List of Figures ................................................................................................................................ ix List of Schemes .............................................................................................................................. xi List of Tables ................................................................................................................................ xv List of Abbreviations ................................................................................................................... xvi CHAPTER 1: INTRODUCTION ................................................................................................ 1 1.1 Glycochemistry Significance and Challenges .......................................................................... 1 1.2 General Aspects of Chemical O-Glycoside Bond Formation ................................................... 2 1.3 Some Common Chemical O-Glycosylation Methods............................................................... 2 1.3.1 The Koenigs-Knorr Method ............................................................................................... 2 1.3.2 The Trichloroacetimidate Method ...................................................................................... 6 1.3.3 Other O-Glycosylation Methods ........................................................................................ 9 1.4 General Mechanism of Chemical O-Glycosylation Reaction ................................................. 10 1.4.1 Mechanistic Studies of Glycosylation .............................................................................. 11 1.4.2 NMR Spectroscopic Studies............................................................................................. 11 1.4.3 Computational Studies ..................................................................................................... 13 1.4.4 Kinetic Isotope Effects ..................................................................................................... 15 1.5 Clock Reactions ...................................................................................................................... 19 1.5.1 Jencks Azide Clock Reaction ........................................................................................... 19 1.5.2 Radical Clocks.................................................................................................................. 20 1.6 Intramolecular Aglycon Delivery ........................................................................................... 21 1.6.1 Silicon Mediated Intramolecular Aglycon Delivery. ....................................................... 23 1.6.2 para-Methoxybenzyl Mediated Intramolecular Aglycon Delivery .................................. 24 1.6.3 Iodonium-mediated Intamolecular Aglycone Delivery.................................................... 28 v 1.7 The Cyclization Concept......................................................................................................... 30 1.8 Previous Studies in Cation Clock Reactions for the Determination of Relative Kinetics in Pyranosyl Sulfoxide Systems and their Limitations. .................................................................... 32 1.9 Problem Statement. ................................................................................................................. 35 1.10 Main Objectives: ................................................................................................................... 36 CHAPTER 2: CATION CLOCK REACTIONS FOR THE DETERMINATION OF RELATIVE KINETICS IN GLYCOSYLATION REACTIONS: APPLICATIONS TO GLUCO AND MANNOPYRANOSYL TRICHLOROACETIMIDATE DONORS ............ 38 2.1 Introduction ............................................................................................................................. 38 2.2 Cation Clock Reactions for the Determination of Relative Kinetics in Glycosylation Reactions: Mannopyranosyl clock system. ..................................................................................................... 40 2.2.1 Synthesis of the 4,6-O-Benzylidene-protected Mannopyranosyl Clock .......................... 40 2.1.2 Reductive Lithiation ......................................................................................................... 42 2.1.3 Clock Cyclization Reaction .............................................................................................. 44 2.1.4 O-Glycoside Formation in Competition with Cyclization ............................................... 45 2.1.5 Kinetic Data..................................................................................................................... 46 2.1.6 C-Glycosylation in competition with cyclization............................................................
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