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

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XV Appendix A11 Crystal data and structure refinement for Palladium(II) Acetylacetonate (144) Empirical formula C10 H14 O4 Pd Formula weight 304.61 Temperature 150(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = 9.965(11) Å �= 90°. Volume 543.1(11) Å 3 Z 2 Density (calculated) 1.863 Mg/m 3 Absorption coefficient 1.699 mm -1 F(000) 304 b = 5.216(6) Å �= 94.859(19)°. c = 10.487(12) Å � = 90°. Crystal size 0.25 x 0.06 x 0.02 mm 3 Theta range for data collection 2.71 to 25.99°. Index ranges -12
A12 Lecture Courses Attended XVI Appendix Advanced Structural Determination Prof. E. G. Hope Clusters Dr. G. Solan Retrosynthetic Analysis Dr. P. Jenkins A13 Organic/Inorganic Seminar Programme 2005 10 th October, Dr. Christopher Frost (University of Bath), Exploring New Strategies in Organic Synthesis via Catalytic Conjugate addition Catalytic Organic Synthesis 17 th October, Prof. Gary Attard (University of Cardiff), Aspects of Chiral Surface Chemisty: an Electrochemical Perspective 26 th October, Prof. R. H. Holm (Harvard University), Structural and Functional Analogues of Molybdenum and Tungsten Oxotransferases/Hydroxylases: What can be Learned? 31 st October, Prof. Matthew Davidson (University of Bath), Metal and Non-Metal Phenolates: Catalysts, Sensors and Surprises 7 th November, Prof. Richard Templar (Imperial College), How Cells Survive - from Lipids to Liquid Crystals 9 th November, Prof. Peter H. Seeberger (ETH, Zurich), Chemical Glycomics: Automated Synthesis of Carbohydrates as a Platform for Biological and Medical Research 14 th November , Dr. Richard Grainger (University of Birmingham), Harnessing Reactive Intermediates for Organic Synthesis 21 st November, Prof. Paul Pringle (University of Bristol), Synergic Effects in Catalysis with Phosphorus (III) Ligands 29 th November, Prof. Tim Softley (University of Oxford), From Highly excited to Ultracold Molecules: Chemical Dynamics in the Extreme
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Synthesis and Comparison of the Rea
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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
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Chapter one
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2 Chapter One potentially explosive
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4 Chapter One ortho-biphenyl trifla
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6 Chapter One 2,10 (3,3-dichlorocam
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8 Chapter One both enantiomers were
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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
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Scheme 1.25 Synthesis of (41)-(44)
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Figure 1.12 �-fluorinated NSAIDs
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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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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: XIV Appendix A10 Crystal data and s
Page 237 and 238: A14 Conferences Attended RSC Organi
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