Synthetic studies on polycyclic indole alkaloids PDF
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Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 2006 Synthetic studies on polycyclic indole alkaloids Tao Wu Iowa State University Follow this and additional works at:https://lib.dr.iastate.edu/rtd Part of theOrganic Chemistry Commons Recommended Citation Wu, Tao, "Synthetic studies on polycyclic indole alkaloids " (2006).Retrospective Theses and Dissertations. 3057. https://lib.dr.iastate.edu/rtd/3057 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please [email protected]. Synthetic studies on polycyclic indole alkaloids by Tao Wu A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Organic Chemistry Program of Study Committee: George A. Kraus, Major Professor Richard C. Larock William S. Jenks Jacob W. Petrich Donald Lee Reynolds Iowa State University Ames, Iowa 2006 Copyright © Tao Wu, 2006. All rights reserved. UMI Number: 3243539 UMI Microform3243539 Copyright2007 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, MI 48106-1346 ii TABLE OF CONTENTS TABLE OF CONTENTS ii LIST OF ABBREVIATION iv ACKNOWLEGEMENT vii ABSTRACT ix GENERAL INTRODUCTION 1 CHAPTER I. HKI 0231A AND HKI 0231B SYNTHESES Introduction 2 Results and Discussion 7 Experimental Section 24 References 47 CHAPTER II. SYNTHESIS OF ABEO-ERGOLINES AND THEIR ANALOGS Introduction 51 Results and Discussion 58 Experimental Section 70 References 85 CHAPTER III. BENZOCYCLOBUTENOL CHEMISTRY Introduction 89 iii Results and Discussion 96 Experimental Section 109 References 123 GENERAL CONCLUSIONS 129 iv LIST OF ABBREVIATIONS AIBN azodiisobutyronitrile app apparent aq aqueous Bn benzyl br broad Bu butyl calcd calculated CSA camphorsulfonic acid δ chemical shift in ppm downfield from Me Si 4 d doublet dd doublet of doublets ddd doublet of doublets of doublets DDQ 2,3-dicyano-5,6-dichloro-1,4-benzoquinone DIPEA diisopropylethylamine DMAP 4-(dimethylamino)pyridine DME glyme DMF N, N-dimethylformamide DMSO dimethyl sulfoxide DPPA diphenylphosphoryl azide dt doublet of triplets EI electron impact equiv equivalent g gram(s) h hour(s) Hz hertz v HMDS potassium bis(trimethylsilyl)amide HMTA hexamethylene tetramine HRMS high-resolution mass spectrum IC inhibitory concentration 50% 50 J coupling constant KHMDS potassium hexamethyldisilazamide L liter(s) LDA lithium diisopropylamide LAH lithium aluminum hydride LiTMP lithium 2,2,6,6-tetramethylpiperidide μ micro m milli, multiplet (NMR) M moles per liter mg milligram(s) mmol millimole(s) mp melting point MHz megahertz min minute(s) mol mole(s) mp melting point m/z mass to charge ratio NMP N-methylpyrrolidinone NMR nuclear magnetic resonance p para PCC pyridinium chlorochromate pH hydrogen ion concentration ppm parts per million vi ppt precipitate PPTS pyridinium 4-toluenesulfonate q quartet quint quintuplet rt room temperature s singlet (NMR) t triplet TBAC tetrabutylammonium chloride TBAF tetrabutylammonium fluoride TBS tert-butyldimethylsilyl TFA trifluoroacetic acid THF tetrahydrofuran TLC thin layer chromatography TMEDA N,N,N',N'-tetramethylethylenediamine TMSCl trimethylsilyl chloride UV ultraviolet vii Acknowledgements First of all, I would like to thank my advisor Professor George A. Kraus for allowing me to join his group and for all his support and advice over the years. He is a brilliant chemist, as well as a wonderful teacher. I will never forget witnessing his many creative ideas and how his training turned me into an organic chemist. I would like to thank Professor Richard C. Larock for his letters of recommendation. Rich is a brilliant chemist. His group has been the place for me to take advice on transition-metal chemistry. And his big book has been the place for me when I need information of organic transformations. I would like to thank Professor William Jenks. I thank him for bringing chemistry with fun to the classroom. As a devoted teacher, the door of his office is always open, even for many of my silly questions. He seems to be always there ready to offer his helpful discussions and suggestions. I would like to thank Professor Jacob Petrich and Professor Donald Reynolds for serving on my POS committee. I thank them for their time and suggestions. I thank Professor John Verkade for his letters of recommendations. I would like to thank all the current and former members of the Kraus group for their friendship. It has been a wonderful experience being part of the group. Special thanks to Dr. Jingqiang Wei, who offered his hands in and outside Gilman Hall; and to Dr. Yi Yuan for his ready support on computer and literature search. My time in the chemistry department has been fun because of the really fantastic people I met here. I thank Dr. Chengxiang Zhou for initiating our discussion group and relaxing tennis time; I thank Zhijian Liu for knowledge of palladium chemistry and I thank Dr. Weiping Su for being a big brother to me. I thank John for his proof-reading on viii my thesis. I also should not forget to thank Jacob and Jesse for their frequent help with my English. My stay here at Iowa State would have been totally different without my wife Liping’s support along the way. Her understanding and patience are essential for the success of my graduate study. I thank my daughter Irene. Her birth brightened my life. And I thank my mother for her endless love and constant encouragement for me to be a better person. Finally, thanks to all of my friends that I have met at Iowa State over the last five years. I will always look back on my time at Iowa State with fondness. Tao Wu Ames, Iowa August 2006
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