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De Novo Synthesis of Phenols

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De Novo Synthesis of Phenols De Novo Synthesis of Phenols Stephen Christopher Johns Thesis submitted in part fulfilment of the degree of Doctor of Philosophy & The Diploma of Imperial College September 2008 Supervised by Professor Donald Craig Department of Chemistry Imperial College London South Kensington London SW7 2AZ 1 Abstract This thesis is divided into three chapters. In the first, the methods currently available for the synthesis of phenols from acyclic precursors are reviewed. The review concentrates on methods that have been used to form a range of phenols and is divided up according to the type of chemistry employed. The second chapter describes the development of a novel route to phenols. Initial optimisation results are described first, followed by the synthesis of a library of phenols. The majority of these have not been reported previously. The attempted extension of this work to the formation of anilines, nitrobenzenes and more highly oxygenated aromatics is also presented. Finally, work towards the synthesis of the aglycone of pseudopterosin A is described, following a route that would utilise the phenol-forming chemistry in a more complex natural product environment. The final section details the experimental procedures used to form the compounds described in section two, along with associated spectroscopic data. 2 Acknowledgements Firstly I would like to thank Prof. Craig for this opportunity and his guidance over the past few years. I would also like to thank Dr Juliet Simpson of GSK for her helpful input and guidance, particularly during my industrial placement. My valued colleagues in the Thorpe lab Henrik, Fred, Simon, Kiyo, Alex, Marcus, Barn and 5 th year guy deserve great thanks for both their advice and friendship during the long days in the lab (especially Thursdays). I am grateful for the efforts of my proofreaders Alex, Yunas, Kiyo, Sophie, Jasprit and Pengfei and for Don’s helpful corrections. Alice, Nige and especially Federica also deserve my thanks. “Though I love you all, I cannot embrace you all. Goodbye my soldiers, goodbye my sons, goodbye my children ” -Rod Steiger (Waterloo 1970 ) Finally I would like to thank my former housemates, Christiana, Sofia and Nouka for putting up with me for so many years and my family for supporting me during my long years at Imperial College. Upper Tier, Major Confusion and Controller. Controller must be thanked among others too numerous to mention for their fantastic music. 3 Contents Abstract ......................................................................................................................................................... 2 Acknowledgements ....................................................................................................................................... 3 Abbreviations ................................................................................................................................................ 8 Stereochemical Notation ............................................................................................................................ 13 1. Review: The Synthesis of Phenols from Acyclic Precursors ............................ 14 1.1. The History of Phenol ....................................................................................................................... 14 1.2. Industrial-Scale Synthesis of Phenol ................................................................................................ 15 1.3. Biosynthesis of Phenols ................................................................................................................... 16 1.4. Uses of Phenols ................................................................................................................................ 17 1.5. Traditional Substituted Phenol Synthesis ........................................................................................ 18 1.6. Formation of Phenols from Acyclic Precursors ................................................................................ 19 1.6.1. Dehydrogenation or Oxidation of Cyclic Compounds ............................................................... 19 1.6.2. Phenols from Dienones or p-Benzoquinones ............................................................................. 20 1.7. Ionic Methods .................................................................................................................................. 21 1.7.1. [3+3] Methods ........................................................................................................................... 21 1.7.2. [4+2] Methods- Robinson Annelation ....................................................................................... 28 1.7.3. 1,5-Diketones ............................................................................................................................ 30 1.7.4. Polyketides ................................................................................................................................ 32 1.7.5. Other Ionic Phenol-forming Methods ....................................................................................... 33 1.8. Pericyclic Methods ........................................................................................................................... 34 1.8.1. Ketene Methods ........................................................................................................................ 34 1.8.2. Generation of Vinyl Ketenes from Cyclobutenones ................................................................... 35 4 1.8.3. Other Methods of Vinyl Ketene Formation ............................................................................... 39 1.8.4. Cyclopropenes ........................................................................................................................... 40 1.8.5. Diels–Alder Methods ................................................................................................................. 44 1.8.6. Furans ........................................................................................................................................ 44 1.8.7. 2-Pyrones .................................................................................................................................. 45 1.8.8. Cyclopentadienes ...................................................................................................................... 46 1.8.9. Enyne–diyne Cycloadditions ...................................................................................................... 46 1.8.10. Enynones ................................................................................................................................. 48 1.8.11. Allenes ..................................................................................................................................... 49 1.8.12. Pauson–Khand ........................................................................................................................ 49 1.8.13. Ring-closing Metathesis .......................................................................................................... 50 1.9. Other Methods ................................................................................................................................. 51 1.10. Summary ........................................................................................................................................ 53 2. Results and Discussion .................................................................................. 54 2.1 Prior Work Within the Group ............................................................................................................ 54 2.2. Trial Phenol-forming Reaction ......................................................................................................... 59 2.2.1. Formation of a Test 1,5-Diketone ............................................................................................. 59 2.2.2. Phenol Formation ...................................................................................................................... 64 2.2.2.1. Base-promoted Aldol .......................................................................................................... 64 2.2.2.2. Acid-promoted Aldol .......................................................................................................... 69 2.2.3. Scale-up of the Phenol-forming Reaction .................................................................................. 71 2.3. Phenol Library Synthesis .................................................................................................................. 72 2.3.1. Synthesis of Allylic Carbonates .................................................................................................. 74 2.3.2. Allylations .................................................................................................................................. 82 2.3.2.1. One-pot 0-1-2 ..................................................................................................................... 83 5 2.3.2.2. Allylations 0-2..................................................................................................................... 84 2.3.2.3. Allylations 0-1..................................................................................................................... 84 2.3.2.4. Allylations 1-2....................................................................................................................
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