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On the Synthesis of Furans and Furan Fatty Acids Andrew W. T. Smith A

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On the Synthesis of Furans and Furan Fatty Acids Andrew W. T. Smith A On the Synthesis of Furans and Furan Fatty Acids Andrew W. T. Smith A Thesis Submitted for the Degree of Doctor of Philosophy At Cardiff University 2012 On the Synthesis of Furans and Furan Fatty Acids Andrew W. T. Smith Declaration This work has not previously been accepted in substance for any degree and is not being concurrently submitted for candidature for any degree. Signed ………………………………………………… (Andrew W. T. Smith) Date…………………………………………………… STATEMENT 1 This thesis is being submitted in partial fulfilment of the requirements for the degree of PhD. Signed ………………………………………………… (Andrew W. T. Smith) Date…………………………………………………… STATEMENT 2 This thesis is the result of my own investigations, except where otherwise stated. Other sources are acknowledged by footnotes giving explicit references. A bibliography is appended. Signed ………………………………………………… (Andrew W. T. Smith) Date…………………………………………………… STATEMENT 3 I hereby give consent for my thesis, if accepted, to be available for photocopying and for inter- library loan, and for the title and summary to be made available to outside organisations. Signed ………………………………………………… (Andrew W. T. Smith) Date…………………………………………………… ii On the Synthesis of Furans and Furan Fatty Acids Andrew W. T. Smith “It was the best of times, it was the worst of times, it was the age of wisdom, it was the age of foolishness, it was the epoch of belief, it was the epoch of incredulity…” Charles Dickens – A Tale of Two Cities “We must not forget that when radium was discovered no one knew that it would prove useful in hospitals. The work was one of pure science. And this is a proof that scientific work must not be considered from the point of view of the direct usefulness of it. It must be done for itself, for the beauty of science, and then there is always the chance that a scientific discovery may become like the radium a benefit for humanity.” Marie Curie “The product of mental labour - science - always stands far below its value, because the labour- time necessary to reproduce it has no relation at all to the labour-time required for its original production.” Karl Marx iii On the Synthesis of Furans and Furan Fatty Acids Andrew W. T. Smith Abstract This thesis describes the use of silver nitrate and iodine to promote 5-endo-dig cyclisations in the synthesis of furans. The oxidation of furylethanols will be discussed as will methods to synthesise furylacetic acids. The total synthesis of a natural product, Plakorsin B will be described along with the total synthesis of the furan fatty acids F5 and F6 as well as giving an overview of their proposed role in Nature. Finally, a new methodology for methylation of halogenated heterocycles will be discussed. iv On the Synthesis of Furans and Furan Fatty Acids Andrew W. T. Smith Acknowledgements I would like to thank my supervisor, Professor David W Knight, for his never-ending support and encouragement and for all his wisdom and guidance and to whom I will forever be indebted. I would like to thank the EPSRC for their financial support. Many thanks to Dr John Brazier, Dr Achim Porzelle, Prof Nick Tomkinson and Dr Ian Morgan for passing on much needed tips and wisdom. I would also like to thank Jess, Dr Ian, Polish Pete, Little Andy, Dr Rhys, Dr Eggo, Dr Tracy, Dr Laura and Dr Damien for helping to make the department a great place to be. I must also acknowledge all the analytical and technical staff especially Dr Rob Jenkins, Robin, Dave, Gaz and Jamie for their hard work and help and also to the secretaries Terrie and Rowlands for the chats, gossip and Christmas parties. I would also like to say a huge thank you to my parents and my brother for all their love and support throughout my life. I love you all! Thanks to all my friends outside of work, but especially Em, Kerzy, Filly & Martin, Jamesy, Andy, Andrew, Mike, Justin, Dave, Danny, Smally and Fordy. I’m extremely privileged to have such ace friends. A very special thank you to Cathy Smith for being a fantastic friend, for encouraging me and giving me the belief I needed to begin this adventure in the first place and, above all, for being the best mother my two beautiful children could ever wish for. My biggest thanks go to my two amazing children, Poppy and Liam. Without their joy and love I could not have completed this thesis. I love you more than words can ever express. v On the Synthesis of Furans and Furan Fatty Acids Andrew W. T. Smith This thesis is dedicated to my two amazing children, Poppy and Liam. vi On the Synthesis of Furans and Furan Fatty Acids Andrew W. T. Smith Detailed Table of Contents DECLARATION......................................................................................................................... ii ABSTRACT.................................................................................................................................iv ACKNOWLEDGEMENTS........................................................................................................ v DEDICATION………............................................................................................................... vi DETAILED TABLE OF CONTENTS.................................................................................... vii ABBREVIATIONS AND ACRONYMS.................................................................................. ix CHAPTER 1: INTRODUCTION.............................................................................................. 1 1.1 Heterocycles…………............................................................................................... 2 1.2 Furan.…………………............................................................................................. 2 1.3 Furans in Nature......................................................................................................... 4 1.4 Traditional Furan Syntheses....................................................................................... 6 1.5 Baldwin’s Rules ……………………......................................................................... 7 1.6 Early Catalytic Synthesis of Furans ………............................................................. 10 1.7 Silver Catalysed Furans Synthesis........................................................................... 12 1.8 Silver-catalysed Cyclisation of 3-alkyne-1,2-diols.................................................. 15 1.9 Gold Catalysed Synthesis of Furans........................................................................ 16 1.10 Iodocyclisation…..………………………............................................................... 18 1.11 Aims of the Project……………………….............................................................. 20 CHAPTER 2: FURAN SYNTHESIS AND 2-FURYLETHANOL OXIDATION.............. 21 2.1 Introduction…………….......................................................................................... 22 2.2 Retrosynthesis of 3-alkyne-1,2-diols....................................................................... 23 2.3 α-Hydroxycarbonyl Pathway................................................................................... 23 2.4 Sonogashira Approach............................................................................................. 24 2.5 Silver-catalysed Cyclisation..................................................................................... 24 2.6 Oxidation of Furylethanol…………………………………………………...……. 26 2.7 Further Investigations into the Oxidation of Furylethanol...................................... 34 2.8 Possible Mechanisms of Jones Oxidation of 2-Furylethanols…………………….. 37 CHAPTER 3: FURYLACETIC ACIDS AND PLAKORSIN B SYNTH..SES.................. 40 3.1 Introduction............................................................................................................ 41 3.2 Plakorsins A and B: Previous Syntheses…………………………………………. 41 3.3 Furylacetic Acid Synthesis…………………………………..…………………… 43 CHAPTER 4: FURAN FATTY ACIDS F5 AND F6............................................................. 47 vii On the Synthesis of Furans and Furan Fatty Acids Andrew W. T. Smith 4.1 What are Furan Fatty Acids..................................................................................... 48 4.2 Isolation and Characterisation………...................................................................... 49 4.3 Distribution in Nature….......................................................................................... 49 4.4 What is Their Role?................................................................................................. 50 4.5 Biosynthesis of F-acids………………................................................................... 54 4.6 Previous Synthetic Routes…………………………............................................... 59 4.7 Retrosynthesis of the Furan Fatty Acids F5 and F6.................................................. 67 4.8 Synthesis of 3-Alkyne-1,2-diol Precursor to F5 and F6 Furan Fatty Acids……….. 69 4.9 Synthesis of F5 Furan Fatty Acid……………………………………………….... 76 4.10 Synthesis of F6 Furan Fatty Acid…………………………………..……………... 84 4.11 Halogen-Metal Exchange using Methyllithium………..………………………. 87 4.12 Conclusions…………….………………………………………………………… 89 CHAPTER 5: EXPERIMENTAL......................................................................................... 90 5.1 General experimental details.................................................................................. 91 5.2 General Procedure for the Synthesis of Furans…………………………………... 93 5.3 Experiments and Data……………………………………………………………. 94 CHAPTER 6: REFERENCES..............................................................................................
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