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

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6.3.2 Preparation of Bis[�-chloro-bis(butenyl-(1,2,3-�)oxy)methyl)benzene] dipalladium (126) 6.3.3 Preparation of Bis[�-chloro-bis(butenyl-(1,2,3-�)-4-methylbenzoate] dipalladium (131) 6.3.4 Preparation of Bis[�-chloro-bis(butenyl-(1,2,3-�)-4-(trifluoromethyl) benzoate] dipalladium (130) 6.3.5 Preparation of Bis[�-chloro-bis(butenyl-(1,2,3-�)-4-fluorobenzoate] dipalladium (127) 6.3.6 Preparation of Bis[�-chloro-bis(butenyl-(1,2,3-�)-3-fluorobenzoate] dipalladium (128) 6.3.7 Preparation of Bis[�-chloro-bis(butenyl-(1,2,3-�)-2-fluorobenzoate] dipalladium (129) 6.3.8 Preparation of ((butenyl-(1,2,3-�)-isoindoline-1,3-dione)bis(triphenyl- phosphine)palladium fluoride (132) 6.3.9 Experimental Data for 2-(buta-1,3-dienyl)isoindoline-1,3-dione (133) 170 6.3.10 General procedure for NMR experiments following reactions of allyl halides with palladium (0) 6.4 Experimental Details for Chapter 4 174 6.4.1 Preparation of Acetylacetonato[(butenyl-(1,2,3-�)-benzoate]palladium (145) 6.4.2 Preparation of Acetylacetonato[(butenyl-(1,2,3-�)-oxy)methyl)benzene] palladium (146) 6.4.3 Preparation of dimethyl 2-(1-(benzoyloxy)but-3-en-2-yl)malonate (148) 175 6.4.4 Preparation of Dimethyl 2-(4-(benzyloxy)but-2-enyl)malonate (147) 176 6.4.5 Preparation of dimethyl 2-(1-(4-fluorobenzoyloxy)but-3-en-2-yl) malonate (150) 6.4.6 Preparation of dimethyl 2-(1-(4-(trifluoromethyl)benzoyloxy)but-3-en-2- yl)malonate (149) 6.4.7 Preparation of 1-fluoro-bis(phenylsulfonyl)methane (140) 177 6.4.8 Preparation of Dimethyl 2-(4-(benzoyloxy)but-2-enyl)malonate (151) 178 6.4.9 Preparation of Dimethyl 2-(4-(benzoyloxy)but-2-enyl)malonate (151) 179 6.4.10 Preparation of Dimethyl 2-(4-(benzoyloxy)but-2-enyl)malonate (151) 179 6.4.11 Preparation of Dimethyl 2-(4-(benzoyloxy)but-2-enyl)malonate (152) 180 vii 165 165 166 167 167 168 169 172 174 174 176 177
6.4.12 Experimental Data for Dimethyl 2-allylmalonate (154) 180 6.4.13 Preparation of dimethyl 2-(1-(3-fluorobenzoyloxy)but-3-en-2-yl) malonate (153) 6.4.14 Preparation of 5-fluoro-5,5-bis(phenylsulfonyl)pent-2-enyl 4-(trifluoromethyl) benzoate (155) 6.4.15 Preparation of Allyl 1-fluoro-bis (phenylsulfonyl)methane (156) 182 6.5 Experimental Details for Chapter 5 183 6.5.1 Preparation of 2,2-difluoro-1-phenylbut-3-en-1-ol (158) 183 6.5.2 Preparation of 2,2-difluoro-1-phenylbut-3-enyl benzoate (159) 183 6.5.3 Preparation of 2,2-difluoro-1-phenylbut-3-enyl 4-fluorobenzoate (160) 184 6.5.4 Preparation of 2,2-difluoro-1-phenylbut-3-enyl 3-fluorobenzoate (161) 185 6.5.5 Preparation of 2,2-difluoro-1-phenylbut-3-enyl 2-fluorobenzoate (162) 186 6.5.6 Preparation of 2,2-difluoro-1-phenylbut-3-enyl 4-(trifluoromethyl) benzoate (163) 6.5.7 Preparation of 2,2-difluoro-1-phenylbut-3-enyl 4-methylbenzoate (164) 188 6.5.8 Preparation of (1-(benzyloxy)-2,2-difluorobut-3-enyl)benzene (165) 188 6.5.9 Preparation of 2,2-difluorobut-3-en-1-ol (174) 189 6.5.10 Preparation of 2,2-difluorobut-3-enyl benzoate (175) 189 6.5.11 Preparation of 2,2-difluorobut-3-enyl 4-fluorobenzoate (176) 190 6.5.12 Preparation of 2,2-difluorobut-3-enyl 3-fluorobenzoate (177) 191 6.5.13 Preparation of 2,2-difluorobut-3-enyl 2-fluorobenzoate (178) 192 6.5.14 Preparation of 2,2-difluorobut-3-enyl 4-methylbenzoate (180) 192 6.5.15 Preparation of 2,2-difluoro-1-(4-(trifluoromethyl)phenyl)but-3-en-1-ol (166) 6.5.16 Preparation of 2,2-difluoro-1-p-tolylbut-3-en-1-ol (167) 194 6.5.17 Preparation of 2,2-difluoro-1-(4-fluorophenyl)but-3-en-1-ol (168) 194 6.5.18 Preparation of 2,2-difluoro-1-(perfluorophenyl)but-3-en-1-ol (169) 195 6.5.19 Preparation of 2,2-difluoro-1-p-tolylbut-3-enyl 4-fluorobenzoate (170) 196 6.5.20 Preparation of 2,2-difluoro-1-(4-(trifluoromethyl)phenyl)but-3-enyl 4- fluoro benzoate (171) 6.5.21 Preparation of 2,2-difluoro-1-(perfluorophenyl)but-3-enyl 4-fluoro benzoate (173) 6.5.22 Preparation of 2,2-difluoro-1-(4-fluorophenyl)but-3-enyl 4-fluoro benzoate (172) viii 181 181 187 193 197 198 199
Page 1 and 2: Synthesis and Comparison of the Rea
Page 3 and 4: Acknowledgements Firstly, I would l
Page 5 and 6: 2.2.2.1.1 Synthesis of 1-(Benzyloxy
Page 7: 6.2.12 Preparation of 2-(4-trimethy
Page 11 and 12: 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
Page 21 and 22: 8 Chapter One both enantiomers were
Page 23 and 24: 10 Chapter One poor to moderate ena
Page 25 and 26: Scheme 1.10 Fluorination of (17) 12
Page 27 and 28: 14 Chapter One fluorine donors, Lew
Page 29 and 30: 1.3 Enantioselective Nucleophilic F
Page 31 and 32: Scheme 1.16 Fluorination of (32) 18
Page 33 and 34: 20 Chapter One (iii) SN2’ type su
Page 35 and 36: 22 Chapter One cytotoxicity in the
Page 37 and 38: 24 Chapter One Manabe and Ishikawa
Page 39 and 40: Scheme 1.25 Synthesis of (41)-(44)
Page 41 and 42: Figure 1.12 �-fluorinated NSAIDs
Page 43 and 44: 1.6 Thesis Outline 30 Chapter One T
Page 45 and 46: 32 Chapter One [26] M. Abdul-Ghani,
Page 47 and 48: [79] M. Schlosser, D. Michael, Z.-W
Page 49 and 50: 2.1 Introduction 2 Synthesis of All
Page 51 and 52: 37 Chapter Two In dehydroxyfluorina
Page 53 and 54: Scheme 2.6 Fluorination with IF5/Et
Page 55 and 56: 41 Chapter Two desired allylic fluo
Page 57 and 58: 43 Chapter Two c) Formation of a su
Page 59 and 60:
Scheme 2.14 Reaction of cis-3-methy
Page 61 and 62:
Substrate (60) (61) (62) (63) R = O
Page 63 and 64:
Alcohol Product Yield (%) Table 2.7
Page 65 and 66:
51 Chapter Two completion. This ena
Page 67 and 68:
53 Chapter Two Chapter Three. Follo
Page 69 and 70:
55 Chapter Two Two allyl alcohols w
Page 71 and 72:
57 Chapter Two The conversion of (8
Page 73 and 74:
Starting substrate (88) (89) (90) (
Page 75 and 76:
Starting substrate (99) (76) (77) (
Page 77 and 78:
63 Chapter Two Both (105) and (104)
Page 79 and 80:
Scheme 2.25 Mechanistic pathway for
Page 81 and 82:
2.3 Conclusions 67 Chapter Two The
Page 83 and 84:
[28] D. F. Taber, J. Am. Chem. Soc.
Page 85 and 86:
Chapter THRee
Page 87 and 88:
72 Chapter Three Kurosawa reacted a
Page 89 and 90:
74 Chapter Three These results demo
Page 91 and 92:
76 Chapter Three More recently, wor
Page 93 and 94:
3.2 Results and Discussion 3.2.1 Re
Page 95 and 96:
80 Chapter Three Starting substrate
Page 97 and 98:
82 Chapter Three Figure 3.4 Crystal
Page 99 and 100:
Scheme 3.12 Oxidative addition of 1
Page 101 and 102:
86 Chapter Three when the reaction
Page 103 and 104:
88 Chapter Three Therefore, from th
Page 105 and 106:
-140 -140 -140 -140 -140 -150 -150
Page 107 and 108:
92 Chapter Three monitored for 80 m
Page 109 and 110:
3.4 References [1] W. T. Dent, R. L
Page 111 and 112:
Chapter Four
Page 113 and 114:
97 Chapter Four nucleophilic substi
Page 115 and 116:
99 Chapter Four Further reactions w
Page 117 and 118:
Figure 4.3 Structure of co-product
Page 119 and 120:
4.2.2 Reactions of palladium cation
Page 121 and 122:
105 Chapter Four substituents on th
Page 123 and 124:
107 Chapter Four The desired produc
Page 125 and 126:
109 Chapter Four The reaction of (1
Page 127 and 128:
111 Chapter Four were both reacted
Page 129 and 130:
[28] D. Landini, A. Maia, A. Rampol
Page 131 and 132:
5.1 Introduction 5 Synthesis and Re
Page 133 and 134:
116 Chapter Five The first enantios
Page 135 and 136:
118 Chapter Five Gem(difluoroallyl)
Page 137 and 138:
120 Chapter Five benzaldehyde, 3-br
Page 139 and 140:
Starting Substrate (76) (77) (78) (
Page 141 and 142:
Starting Substrate Product Yield (%
Page 143 and 144:
5.2.4 Synthesis of Allylic Difluori
Page 145 and 146:
5.2.5 Metal-mediated synthesis of 3
Page 147 and 148:
130 Chapter Five process. [40] Unfo
Page 149 and 150:
132 Chapter Five compounds were pur
Page 151 and 152:
134 Chapter Five [30] H. L. Sham, N
Page 153 and 154:
6.1 General Experimental Procedures
Page 155 and 156:
6.2 Experimental Details for Chapte
Page 157 and 158:
139 Chapter Six (1 g, 0.75 cm 3 , 6
Page 159 and 160:
6.2.7 Preparation of allyl 4-(trifl
Page 161 and 162:
6.2.10 Preparation of (3-[1,3]Dioxa
Page 163 and 164:
145 Chapter Six reaction mixture wa
Page 165 and 166:
147 Chapter Six mg, 1.1 mmol), ally
Page 167 and 168:
149 Chapter Six 260.3 Hz, ArCF), 16
Page 169 and 170:
6.2.22 Preparation of 2-fluorobut-3
Page 171 and 172:
6.2.25 Preparation of 2-fluorobut-3
Page 173 and 174:
6.2.28 Preparation of 2-hydroxybut-
Page 175 and 176:
157 Chapter Six 1 JCF = 253.5 Hz, A
Page 177 and 178:
159 Chapter Six drying under high v
Page 179 and 180:
6.2.37 Preparation of 2-chlorobut-3
Page 181 and 182:
6.2.40 Preparation of 2-chlorobut-3
Page 183 and 184:
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 215 and 216:
Page 217 and 218:
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 and 236:
A12 Lecture Courses Attended XVI Ap
Page 237 and 238:
A14 Conferences Attended RSC Organi
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