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Synthesis and Reactivity of Cyclopropanes and Cyclopropenes

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Synthesis and Reactivity of Cyclopropanes and Cyclopropenes Loughborough University Institutional Repository Synthesis and reactivity of cyclopropanes and cyclopropenes This item was submitted to Loughborough University's Institutional Repository by the/an author. Additional Information: • A Doctoral Thesis. Submitted in partial fulllment of the requirements for the award of Doctor of Philosophy of Loughborough University. Metadata Record: https://dspace.lboro.ac.uk/2134/9032 Publisher: c Hayley Watson Please cite the published version. This item was submitted to Loughborough’s Institutional Repository (https://dspace.lboro.ac.uk/) by the author and is made available under the following Creative Commons Licence conditions. For the full text of this licence, please go to: http://creativecommons.org/licenses/by-nc-nd/2.5/ Synthesis and reactivity of Cyclopropanes and Cyclopropenes by Hayley T. A. Watson A Doctoral Thesis Submitted in partial fulfilment of the requirements For the award of Doctor of Philosophy of Loughborough University (June 2011) © by Hayley Watson (2011) ABSTRACT Activated cyclopropanes have been extensively used in synthetic chemistry as precursors for cycloaddition reactions. The rationale behind this is their ability to undergo ring- opening when activated by a Lewis acid, this can be enhanced further by the presence of a carbocation stabilising group like electron-rich aromatics. The stabilised dipole formed after ring opening can be trapped with suitable electrophiles such as imines and aldehydes via a [3+2] cycloaddition reaction. This results in the synthesis of pyrrolidines and tetrahydrofurans in excellent yields but moderate diastereoselectivity. Similarly, 6- membered heterocycles can be formed via a [3+3] cycloaddition reaction of activated cyclopropanes with nitrones. Now to extend the scope of the methodology, a [3+3] dipolar cycloaddition has been developed using activated 2,3 disubstituted cyclopropane diesters to access a range of highly functionalised oxazines in moderate to good yields (50-75%) and with reasonable diastereoselectivity. The use of activated symmetrical disubstituted cyclopropanes afforded the desired oxazines in a regio- and diastereocontrolled manner, while the use of unsymmetrical cyclopropanes significantly reduced the diastereoselectivity of the reaction. The stereochemistry outcome of the reaction developed was determined by nOe analyses and X-ray diffraction structures could be recorded in some examples. A new methodology has also been developed to gain access to novel N- heterocyclic- and phenol- substituted cyclopropanes in one step from the corresponding cyclopropene via a conjugated addition. Key Words: Cycloaddition, cyclopropane, cyclopropene, nucleophilic addition, oxazine, ring-opening i ACKNOWLEDGEMENTS I would like to dedicate my thesis to my beloved auntie Shirley who sadly lost her life to breast cancer 2 years ago. Throughout my life Shirley was always there to guide me through good and bad times and told me to make the most of my life in whatever way possible. I also would not have been able to get through my degree and PhD without the loving support of my Mum, Dad and brother Jake and I thank you all for helping me through these times. I would like to acknowledge and thank the following people for their guidance and help during my PhD; First of all I would like to thank my supervisor Dr Steve Christie for giving me the opportunity to do a PhD and the guidance he has given me throughout the three years. I also appreciate the support given to me by my industrial supervisor Dr Julie Rielly of Astra Zeneca, who provided me with her expertise and the experience of working in the pharmaceutical industry. I also thank the technical team within the department and a special thank you goes to Mark Edgar for his help in solving complex NMR spectra, Mark Elsegood for his help with X- ray diffraction and Alistair Daily for his day to day running of the laboratory. For friendship and entertainment I thank the people in F001 and F009 labs past and present, especially Claire, Stephen, Jess, Laura and Tom who provided me with the necessary entertainment to get through the day. I would also like to thank my friend Silvia Anton for moral support and making the last two years of my PhD enjoyable. In moral support and the writing of my thesis I whole heartedly thank my boyfriend Eric Allart for being there every step of the way and without his guidance and expertise I would never have completed. I would also like to thank Tom for his help in reviewing my thesis. ii TABLE OF CONTENT 1. INTRODUCTION 1 1.1. BACKGROUND ON THREE-MEMBERED RINGS 1 1.1.1. BONDING PROPERTIES OF CYCLOPROPANES 1 1.1.2. THE CHEMISTRY OF CYCLOPROPENES 2 1.1.3. SYNTHESIS OF CYCLOPROPENES 3 1.2. REACTIONS OF CYCLOPROPENES 4 1.2.1. CARBOMETALATION OF CYCLOPROPENES 4 1.2.2. FACIALLY SELECTIVE AND HYDROXYL DIRECTED CARBOMETALATION OF CYCLOPROPENES 8 1.2.3. USE OF ESTER FUNCTIONALITIES AS SYN-DIRECTING GROUPS IN CARBOMETALATION REACTIONS 15 1.2.4. ORGANOLITHIUM CARBOMETALATION 17 1.2.5. ORGANOCOPPER MEDIATED CARBOMETALATION 19 1.2.6. TIN MEDIATED HYDROMETALLATION ONTO CYCLOPROPENES 20 1.2.7. SELECTIVE ADDITION OF HETEROATOMS TO CYCLOPROPENES 22 1.2.8. ADDITION TO CONJUGATED ALKYNYLCYCLOPROPENES 24 1.2.9. NUCLEOPHILIC SUBSTITUTIONS OF BROMOCYCLOPROPANES 27 1.2.10. RING-OPENING OF CYCLOPROPROPENES 28 1.3. CYCLOADDITION REACTIONS ONTO CYCLOPROPANES 30 1.3.1. DISCOVERY AND APPLICATION 30 1.3.2. [3+2] DIPOLAR CYCLOADDITION REACTIONS 32 1.3.3. USE OF [3+2] DIPOLAR CYCLOADDITIONS IN THE SYNTHESIS OF OXAZINE DERIVATIVES 33 1.3.4. INTRAMOLECULAR [3+2] CYCLOADDITION REACTIONS 40 1.3.5. SYNTHESIS OF TETRAHYDROFURAN DERIVATIVES VIA THE [3+2] CYCLOADDITION REACTION 42 1.3.6. APPLICATIONS OF [3+2] CYCLOADDITION REACTION TO NATURAL PRODUCTS 44 1.3.7. SYNTHESIS OF PYRROLIDINES AND PYRAZOLINES DERIVATIVES VIA THE CYCLOADDITION REACTION 46 1.3.8. USE OF DI-COBALT COMPLEXES IN THE [3+2] CYCLOADDITION REACTION WITH CYCLOPROPANES 53 1.3.9. A RADICAL APPROACH TOWARDS THE CYCLOADDITION OF ACTIVATED CYCLOPROPANE DIESTERS 57 2. RESULTS AND DISCUSSION 60 2.1. ATTEMPTED SYNTHESIS OF CYCLOPROPYL BORONATES 61 2.1.1. FIRST ATTEMPT-STARTING FROM VINYL BORONIC ACID 61 2.1.2. SECOND ATTEMPT – HYDROBORATION OF CYCLOPROPENES 63 iii 2.2. THIRD ATTEMPT-STARTING FROM 1-ALKYNYLDIISOPROPOXYBORANES 66 2.3. SYNTHESIS OF 2,3 DISUBSTITUTED CYCLOPROPANE DIESTERS 68 2.4. CYCLOADDITIONS WITH DI-SUBSTITUTED CYCLOPROPANES 72 2.4.1. SYNTHESIS OF NITRONES 73 2.4.2. [3+3] CYCLOADDITIONS 74 2.5. SYNTHESIS OF N-HETEROCYCLE SUBSTITUTED CYCLOPROPANE DIESTERS 82 2.6. SYNTHESIS OF N-HETEROCYCLE SUBSTITUTED CYCLOPROPANE MONOESTERS 89 2.7. USE OF ELECTRON RICH AND DEFICIENT CYCLOPROPENES IN THE ADDITION REACTION 90 2.8. ADDITION OF PHENOLS TO ACTIVATED CYCLOPROPENES 98 2.9. ATTEMPTED CYCLOADDITIONS WITH N-HETEROCYCLE SUBSTITUTED CYCLOPROPANES 104 2.10. REPLACEMENT OF THE DIESTER WITH A MONO TRIFLUOROMETHYL GROUP 107 2.11. ATTEMPTED CYCLOADDITIONS REACTIONS WITH NITRO SUBSTITUTED CYCLOPROPANES 110 2.12. SYNTHESIS OF NITROCYCLOPROPANES 111 2.13. ATTEMPTED INTRAMOLECULAR CYCLOADDITIONS WITH NITROCYCLOPROPANES 112 3. CONCLUSION 119 4. EXPERIMENTAL 123 5. REFERENCES 190 6. APPENDICES 196 6.1. APPENDIX I: X-RAY CRYSTALLOGRAPHIC DATA FOR 176A 196 6.2. APPENDIX II: X-RAY CRYSTALLOGRAPHIC DATA FOR 176E 207 6.3. APPENDIX III: X-RAY CRYSTALLOGRAPHIC DATA FOR 182A 221 6.4. APPENDIX IV: X-RAY CRYSTALLOGRAPHIC DATA FOR 187A 239 6.5. APPENDIX V: X-RAY CRYSTALLOGRAPHIC DATA FOR 191E 246 6.6. APPENDIX VI: X-RAY CRYSTALLOGRAPHIC DATA FOR 194 252 6.7. APPENDIX VII: X-RAY CRYSTALLOGRAPHIC DATA FOR 198A 262 iv ABBREVIATIONS Ac = acetyl BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl bp = boiling point Bn = benzyl group nBuLi or BuLi = butyl lithium °C = degrees Celcius cat = catalytic CH2Cl2 = dichloromethane cm–1 = wave number CuCN = copper(I) cyanide δ = chemical shift d = doublet 1,2-DCE = 1,2-dichloroethane dd = doublet of double d.e. = diastereoisomeric excess DMS = dimethylsulfide DMF = N,N-dimethylformamide DMSO = dimethylsulfoxide d.r. = diastereoisomeric ratio e- = electron e.e. = enantiomeric excess EI = electron impact ionisation eq = equivalent(s) ESI = electronspray ionisation Et = ethyl EtOH = ethanol Et2O = diethyl ether FAB = fast atom bombardment FeCl3 = iron(III) chloride g = gram v h = hour Hz = hertz IR = infra-red K2CO3 = potassium carbonate KOH = potassium hydroxide LiAlH4 = lithium aluminium hydride m = multiplet Me = methyl MeI = methyl iodide MEM = β-methoxyethoxymethyl ether MeOH = methanol MeCN = acetonitrile MHz = megahertz min = minutes mL = millilitre mmol = millimole MOM = methoxymethyl ether MO = molecular orbital mp = melting point ms = 4 Å molecular sieves Ms = mesyl MS = mass spectroscopy m/z = mass to charge ratio NH4Cl = ammonium chloride NMR = nuclear magnetic resonance nOe = nuclear Overhauser effect Nu = Nucleophile OTf = trifluoromethanesulfonyl P = protecting goup p- = para-substituted Ph = phenyl ppm = parts per million iPr = iso-propyl r.t. = room temperature vi Rh2(OAc)4 = rhodium(II) acetate dimer Pd(OAc)2 = palladium(II) acetate s = singlet SEM = [2-(trimethylsilyl)ethoxy]methyl SM = starting material t = triplet, time T = temperature tBu = tertiary-butyl Tf = trifluoromethanesulfonyl THF = tetrahydrofuran THP = tetrahydropyran TLC = thin layer chromatography TMEDA = tetramethylethylenediamine TMS = trimethylsilyl μL = microlitre vii 1. Introduction 1.1. Background on three-membered rings 1.1.1. Bonding Properties of Cyclopropanes Three-membered ring systems are very important building blocks
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