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

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5.4 References [1] M. J. Tozer, T. F. Herpin, Tetrahedron 1996, 52, 8619. [2] S.-H. An, M. Bobek, Tetrahedron Lett. 1986, 27, 3219. [3] W. J. Middleton, E. M. Bingham, J. Org. Chem. 1980, 45, 2883. [4] S. Stavber, Z. Koren, M. Zupan, Synlett 1994, 265. 133 Chapter Five [5] A. J. Bloodworth, K. J. Bowyer, J. C. Mitchell, Tetrahedron Lett. 1987, 28, 5347. [6] J. P. Praly, G. Descotes, Tetrahedron Lett. 1987, 28, 1405. [7] R. E. Banks, N. J. Lawrence, A. L. Popplewell, J. Chem. Soc., Chem. Commun. 1994, 343. [8] G. Resnati, D. D. DesMarteau, J. Org. Chem. 1992, 57, 4281. [9] W. Ying, D. D. DesMarteau, Y. Gotoh, Tetrahedron 1996, 52, 15. [10] J. Fried, E. A. Hallman, Tetrahedron Lett. 1984, 25, 2301. [11] T. Ishihara, M. Yamanaka, T. Ando, Chem. Lett. 1984, 1165. [12] G. Du<strong>the</strong>uil, S. Couve-Bonnaire, X. Pannecoucke, Angew. Chem., Int. Ed. Engl. 2007, 46, 1290. [13] T. Narumi, A. Niida, K. Tomita, S. Oishi, A. Otaka, H. Ohno, N. Fujii, Chem. Commun. 2006. [14] Y. Nakamura, M. Okada, A. Sato, H. Horikawa, M. Koura, A. Saito, T. Taguchi, Tetrahedron 2005, 61, 5741. [15] T. Allmendinger, E. Felder, E. Hungerbuhler, Tetrahedron Lett. 1990, 31, 7301. [16] P. Bey, J. R. McCarthy, I. A. McDonald, ACS Symp. Ser. 1991, 456, 105. [17] O. Yokokoji, T. Shimizu, S. Kumai, Chem. Abstr. 1996, 124, 316586. [18] M. Kuroboshi, T. Ishihara, Tetrahedron Lett. 1987, 28, 6481. [19] M. Kuroboshi, T. Ishihara, Bull. Chem. Soc. Jap. 1990, 63, 428. [20] R. W. Lang, B. Schaub, Tetrahedron Lett. 1988, 29, 2943. [21] Y. Shen, M. Qi, J. Fluorine Chem. 1994, 67, 229. [22] T. T. Curran, J. Org. Chem. 1993, 58, 229. [23] J. M. Altenburger, D. Schirlin, Tetrahedron Lett. 1991, 32, 7255. [24] Y. Yamana, T. Ishihara, T. Ando, Tetrahedron Lett. 1983, 24, 507. [25] O. Kitagawa, T. Taguchi, Y. Kobayashi, Tetrahedron Lett. 1988, 29, 1803. [26] M. Braun, A. Vonderhagen, D. Waldmuller, Liebigs. Ann. 1995, 1447. [27] T. Tsukamoto, T. Kitazume, J. Chem. Soc., Chem. Commun. 1992, 540. [28] T. Tsukamoto, T. Kitazume, J. Chem. Soc., Perkin Trans 1 1993, 1177. [29] V. P. Kukhar, V. A. Soloshonok, Fluorine-containing Amino Acids, Chichester, 1995.
134 Chapter Five [30] H. L. Sham, N. E. Wideburg, S. G. Spanton, W. E. Kohlbrenner, D. A. Betebenner, D. J. Kempf, D. W. Norbeck, J. J. Plattner, J. W. Erickson, J. Chem. Soc., Chem.Commun. 1991, 110. [31] H. L. Sham, C. A. Rempel, H. Stein, J. Cohen, J. Chem. Soc., Chem. Commun. 1990, 904. [32] D. Seyferth, K. R. Wursthorn, J. Organomet. Chem. 1979, 182, 455. [33] Z.-Y. Yang, D. J. Burton, J. Fluorine Chem. 1989, 44, 339. [34] Z.-Y. Yang, D. J. Burton, J. Org. Chem. 1991, 56, 1037. [35] M. Kirihara, T. Takuwa, S. Takizawa, T. Momose, H. Nemoto, Tetrahedron 2000, 56, 8275. [36] C. Audouard, J. Fawcett, G. Griffiths, J. Percy, S. Pintat, C. Smith, Org. Biomol. Chem. 2004, 2, 528. [37] K. Nakamura, K. Takenaka, Tetrahedron: Asymmetry 2002, 13, 415. [38] S. Elshani, E. Kobzar, R. A. Bartsch, Tetrahedron 2000, 56, 3291. [39] Y. Wu, J. Gao, Org. Lett. 2008, 10, 1533. [40] T. Narumi, K. Tomita, E. Inokuchi, K. Kobayashi, S. Oishi, H. Ohno, N. Fujii, Org. Lett. 2007, 9, 3465. [41] W. Qiu, D. J. Burton, J. Fluorine Chem. 1993, 65, 143.
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 and 8:
6.2.12 Preparation of 2-(4-trimethy
Page 9 and 10:
6.4.12 Experimental Data for Dimeth
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
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8 Chapter One both enantiomers were
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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
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Scheme 1.16 Fluorination of (32) 18
Page 33 and 34:
20 Chapter One (iii) SN2’ type su
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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
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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
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43 Chapter Two c) Formation of a su
Page 59 and 60:
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
Page 73 and 74:
Starting substrate (88) (89) (90) (
Page 75 and 76:
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
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
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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
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: 132 Chapter Five compounds were pur
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
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191 Chapter Six (d, 1 JCF = 255.0 H
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193 Chapter Six layer separated and
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195 Chapter Six Hz, 4 JHF = 3.2 Hz,
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197 Chapter Six 6.5.20 Preparation
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199 Chapter Six 6.5.22 Preparation
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Appendix
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II Appendix Second generation Grubb
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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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