Synthesis and Comparison of the Reactivity of Allyl Fluorides and ...

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XVII Appendix 5 th December, Prof. Tom Simpson (University of Bristol), Fungal Polyketides: Tales of the Unexpected 7 th December, Dr Yasuhisa Ikeda (Research laboratory for Nuclear Reactors), Studies on Solute-Solvent Interactions in Supercritical CO2 by Using Raman Spectroscopy and Applications of Ionic Liquids to Pyrochemical Reprocessing Methods 2006 22 nd February - Leicester Half-day Symposium Dr. Darren Dixon (University of Manchester), Chiral Water from Chiral Relays: Stereocontrol in the Oxy-Michael and Related Reactions Dr. Bruno Linclau (University of Southampton), Novel Approaches for the Enantioselective Total Synthesis of Steroids Prof. Tony Barrett (Imperial College), Recent Advances in Methods for Parallel Synthesis 6 th March, Prof. M. Sodeoka (Tohoku University), Enantioselective Catalysis Based on Palladium Enolate Chemistry 22 nd November - Leicester Green Chemistry Symposium Dr Neil Winterton (University of Liverpool), Green Chemistry and Ionic Liquids Dr Peter Licence (University of Nottingham), Ionic Liquids In Vacuo Dr Paul Watts (University of Hull), Application of Micro-reactors for Improving Atom Efficient Chemical Reactions 2007 30 th April - Metals In Medicine Symposium Dr Sofia I Pascu (University of Oxford), Designing Small-Molecule Based Probes for in vitro Fluorescence Imaging Prof. Nils Metzler-Nolte (Ruhr-Universitat Bochum), Labelling of Bioactive Peptides with Organometallic Compounds: From Solid Phase Synthesis to Biomedical Applications Dr Gareth Williams (University of Durham), Sensing and Imaging with Cells Permeable Luminescent Platinum Complexes Prof. Chris Orvig (University of British Columbia), Carbohydrate Conjugates in Medicinal Inorganic Chemistry
A14 Conferences Attended RSC Organic Division, University of Warwick, April 2006 Organic Synthesis Symposium, University of Loughborough, March 2007 RSC Organic Division, University of Nottingham, April 2007 XVIII Appendix RSC Fluorine Subject Group Postgraduate Meeting, University of Leicester, September 2007 AstraZeneca R&D Charnwood & Loughborough University Organic Synthesis Symposium, October 2007 An Introduction to Process Chemistry, GSK Stevenage, October 2007 Dalton Division Midlands Postgraduate Symposium, University of Warwick, March 2008 RSC Industry Tour, July 2008 RSC Fluorine Subject Group Postgraduate Meeting, Newcastle University, September 2008 A15 Presentations Presentation – “Transition Metal Centred Fluorination”- University of Leicester. Presentation – “Synthesis of Metal Allyl Complexes”- University of Leicester. Poster – “Transition Metal Centred Fluorination.” K. Rakkar and E.G. Hope. Presented at postgraduate fluorine subject group meeting, Dalton division midlands postgraduate symposium and RSC industry tour. Poster – “Synthesis of Metal allyl Complexes.” K. Rakkar and E.G. Hope. Presented at postgraduate fluorine subject group meeting
Page 1 and 2:
Synthesis and Comparison of the Rea
Page 3 and 4:
Acknowledgements Firstly, I would l
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2.2.2.1.1 Synthesis of 1-(Benzyloxy
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6.2.12 Preparation of 2-(4-trimethy
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6.4.12 Experimental Data for Dimeth
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AgF ap Bn Bz CsF d DAST dba DCM DME
Page 13 and 14:
Chapter one
Page 15 and 16:
2 Chapter One potentially explosive
Page 17 and 18:
4 Chapter One ortho-biphenyl trifla
Page 19 and 20:
6 Chapter One 2,10 (3,3-dichlorocam
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8 Chapter One both enantiomers were
Page 23 and 24:
10 Chapter One poor to moderate ena
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Scheme 1.10 Fluorination of (17) 12
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14 Chapter One fluorine donors, Lew
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1.3 Enantioselective Nucleophilic F
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Scheme 1.16 Fluorination of (32) 18
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20 Chapter One (iii) SN2’ type su
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22 Chapter One cytotoxicity in the
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24 Chapter One Manabe and Ishikawa
Page 39 and 40:
Scheme 1.25 Synthesis of (41)-(44)
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Figure 1.12 �-fluorinated NSAIDs
Page 43 and 44:
1.6 Thesis Outline 30 Chapter One T
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32 Chapter One [26] M. Abdul-Ghani,
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[79] M. Schlosser, D. Michael, Z.-W
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2.1 Introduction 2 Synthesis of All
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37 Chapter Two In dehydroxyfluorina
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Scheme 2.6 Fluorination with IF5/Et
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41 Chapter Two desired allylic fluo
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43 Chapter Two c) Formation of a su
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Scheme 2.14 Reaction of cis-3-methy
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Substrate (60) (61) (62) (63) R = O
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Alcohol Product Yield (%) Table 2.7
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51 Chapter Two completion. This ena
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53 Chapter Two Chapter Three. Follo
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55 Chapter Two Two allyl alcohols w
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57 Chapter Two The conversion of (8
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Starting substrate (88) (89) (90) (
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Starting substrate (99) (76) (77) (
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63 Chapter Two Both (105) and (104)
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Scheme 2.25 Mechanistic pathway for
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2.3 Conclusions 67 Chapter Two The
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[28] D. F. Taber, J. Am. Chem. Soc.
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Chapter THRee
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72 Chapter Three Kurosawa reacted a
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74 Chapter Three These results demo
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76 Chapter Three More recently, wor
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3.2 Results and Discussion 3.2.1 Re
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80 Chapter Three Starting substrate
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82 Chapter Three Figure 3.4 Crystal
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Scheme 3.12 Oxidative addition of 1
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86 Chapter Three when the reaction
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88 Chapter Three Therefore, from th
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-140 -140 -140 -140 -140 -150 -150
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92 Chapter Three monitored for 80 m
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3.4 References [1] W. T. Dent, R. L
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Chapter Four
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97 Chapter Four nucleophilic substi
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99 Chapter Four Further reactions w
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Figure 4.3 Structure of co-product
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4.2.2 Reactions of palladium cation
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105 Chapter Four substituents on th
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107 Chapter Four The desired produc
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109 Chapter Four The reaction of (1
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111 Chapter Four were both reacted
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[28] D. Landini, A. Maia, A. Rampol
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5.1 Introduction 5 Synthesis and Re
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116 Chapter Five The first enantios
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118 Chapter Five Gem(difluoroallyl)
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120 Chapter Five benzaldehyde, 3-br
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Starting Substrate (76) (77) (78) (
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Starting Substrate Product Yield (%
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5.2.4 Synthesis of Allylic Difluori
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5.2.5 Metal-mediated synthesis of 3
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130 Chapter Five process. [40] Unfo
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132 Chapter Five compounds were pur
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134 Chapter Five [30] H. L. Sham, N
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6.1 General Experimental Procedures
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6.2 Experimental Details for Chapte
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139 Chapter Six (1 g, 0.75 cm 3 , 6
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6.2.7 Preparation of allyl 4-(trifl
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6.2.10 Preparation of (3-[1,3]Dioxa
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145 Chapter Six reaction mixture wa
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147 Chapter Six mg, 1.1 mmol), ally
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149 Chapter Six 260.3 Hz, ArCF), 16
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6.2.22 Preparation of 2-fluorobut-3
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6.2.25 Preparation of 2-fluorobut-3
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6.2.28 Preparation of 2-hydroxybut-
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157 Chapter Six 1 JCF = 253.5 Hz, A
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159 Chapter Six drying under high v
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6.2.37 Preparation of 2-chlorobut-3
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6.2.40 Preparation of 2-chlorobut-3
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6.3.2 Preparation of Bis[�-chloro
Page 185 and 186: 167 Chapter Six 6.3.5 Preparation o
Page 187 and 188: 169 Chapter Six 4 JHH = 1.2 Hz, ArH
Page 189 and 190: Time (minutes) 4 11 18 25 Table 6.2
Page 191 and 192: Time (minutes) 19 F{ 1 H} (ppm) Tim
Page 193 and 194: 175 Chapter Six suspension of sodiu
Page 195 and 196: 177 Chapter Six Hz, Ha), 5.19 (1H,
Page 197 and 198: 6.4.9 Preparation of Dimethyl 2-(4-
Page 199 and 200: 181 Chapter Six 6.4.13 Preparation
Page 201 and 202: 6.5 Experimental Details for Chapte
Page 203 and 204: 185 Chapter Six CHCH2), 133.9 (d, 3
Page 205 and 206: 187 Chapter Six 6.5.6 Preparation o
Page 207 and 208: 189 Chapter Six (5 mg, 0.27 mmol) a
Page 209 and 210: 191 Chapter Six (d, 1 JCF = 255.0 H
Page 211 and 212: 193 Chapter Six layer separated and
Page 213 and 214: 195 Chapter Six Hz, 4 JHF = 3.2 Hz,
Page 219 and 220: Appendix
Page 221 and 222: II Appendix Second generation Grubb
Page 223 and 224: IV Appendix mixture was stirred at
Page 225 and 226: VI Appendix stirred at room tempera
Page 227 and 228: VIII Appendix The organic phase was
Page 229 and 230: X Appendix A6 Crystal data and stru
Page 231 and 232: XII Appendix A8 Crystal data and st
Page 233 and 234: XIV Appendix A10 Crystal data and s
Page 235: A12 Lecture Courses Attended XVI Ap
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