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References 47 16. Rong, X.X., Pan, H.-Q., Dolbier, Jr., W.R., and Smart, B.E., J. Am. Chem. Soc., 1994, 116, 4521. 17. Shtarev, A.B., Dolbier, Jr., W.R., and Smart, B.E., J. Am. Chem. Soc., 1999, 121, 2110. 18. Dolbier, Jr., W.R., and Li, A.-R., J. Chem. Soc., Perkin Trans. 2, 1998, 79. 19. Baruch, G., and Horowitz, A., J. Phys. Chem., 1980, 84, 2535. 20. Chatgilialoglu, C., Ferreri, C., Lucarini, M., Venturini, A., and Zavitsas A.A., Chem. Eur. J., 1997, 3, 376. 21. Lucarini, M., Marchesi, E., Pedulli, G.F., and Chatgilialoglu, C., J. Org. Chem., 1998, 63, 1687. 22. Varlamov, V.T., Denisov, E.T., and Chatgilialoglu, C., J. Org. Chem., 2001, 66, 6317. 23. Chatgilialoglu, C., Scaiano, J.C ., and Ingold, K.U., Organometallics, 1982, 1, 466. 24. Chatgilialoglu, C., Ingold, K.U., Lusztyk, J., Nazran, A.S., and Scaiano, J.C., Organometallics, 1983, 2, 1332. 25. Lusztyk, J., Maillard, B., and Ingold, K.U., J. Org. Chem., 1986, 51, 2457. 26. Chatgilialoglu, C., and Rossini, S., Bull. Soc. Chim. Fr., 1988, 298. 27. Chatgilialoglu, C., Guerra, M., Guerrini, A., Seconi, G., Clark, K.B., Griller, D., Kanabus-Kaminska, J., and Martinho-Simões, J.A., J. Org. Chem., 1992, 57, 2427. 28. Lee, Y.E., and Choo, K.Y., Int. J. Chem. Kinet., 1986, 18, 267. 29. Chatgilialoglu, C., Timokhin, V.I., Zaborovskiy, A.B., Lutsyk, D.S., and Prystansky, R.E., J. Chem. Soc., Perkin Trans. 2, 2000, 577. 30. Chatgilialoglu, C., Malatesta, V., and Ingold, K.U., J. Phys. Chem., 1980, 84, 3597. 31. Doba, T., and Ingold, K.U., J. Am. Chem. Soc., 1984, 106, 3958. 32. Chateauneuf, J., Lusztyk, J., and Ingold, K.U., J. Am. Chem. Soc., 1988, 110, 2886. 33. Roberts, B.P., Chem. Soc. Rev., 1999, 28, 25. 34. Cai, Y., and Roberts, B.P., J. Chem. Soc., Perkin Trans. 2, 2002, 1858. 35. Müller, U., Helmstreit, W., and Timpe, H.-J., J. Photochem Photobiol. A: chem., 1989, 50, 1. 36. Arthur, N.L., and Miles, L.A., J. Chem. Soc., Faraday Trans., 1998, 94, 1077. 37. Yu, X., Li, S.-M., Xu, Z.-F., Li, Z.-S., and Sun, C.-C., J. Phys. Chem. A, 2001, 105, 7072. 38. Arthur, N.L., Potzinger, P., Reimann, B., and Steenbergen, H-P., J. Chem. Soc., Faraday Trans., 1989, 85, 1447. 39. Dakternieks, D., Henry, D.J., and Schiesser, C.H. J. Chem. Soc., Perkin Trans. 2, 1998, 591. 40. Zavitsas, A.A., and Chatgilialoglu, C., J. Am. Chem. Soc., 1995, 117, 10645. 41. Zavitsas, A.A., J. Am. Chem. Soc., 1998, 120, 6578. 42. Roberts, B.P., and Steel, A.J., J. Chem. Soc., Perkin Trans. 2, 1994, 2155. 43. Denisov, E.T., Russ. Chem. Bull., 1998, 47, 1274.
4 Reducing Agents 4.1 GENERAL ASPECTS OF RADICAL CHAIN REACTIONS The use of free-radical reactions in organic synthesis started with the reduction of functional groups. The purpose of this chapter is to give an overview of the relevance of silanes as efficient and effective sources for facile hydrogen atom transfer by radical chain processes. A number of reviews [1–7] have described some specific areas in detail. Reaction (4.1) represents the reduction of a functional group by silicon hydride which, in order to be a radical chain process, has to be associated with initiation, propagation and termination steps of the radical species. Scheme 4.1 illustrates the insertion of Reaction (4.1) in a radical chain process. RZ þ R 0 3SiH !RH þ R0 3SiZ (4:1) A large number of compounds are known to decompose thermally or photolytically to generate free radicals (see Section 4.2). These radicals (In:) participate in the initiation step by abstracting a hydrogen atom from the reducing SiH. In the propagation steps, the removal of the functional group Z in agent R0 3 the organic substrate takes place by action of R0 3Si: radical via a reactive intermediate or a transition state represented by [RZ(:)SiR0 3 ]. A site-specific radical R: is generated, which then reacts with the silicon hydride and gives the reduced product, together with ‘fresh’ R0 3Si: radicals to continue the chain. Chain reactions terminate by radical–radical combination or disproportionation reactions, with the general concept that the more remote the termination reactions the more efficient is the chain reaction. Kinetically speaking, to be efficient the rate of chain transfer steps between radicals and starting materials must be higher than that of chain termination steps between radicals. The Organosilanes in Radical Chemistry C. Chatgilialoglu # 2004 John Wiley & Sons, Ltd ISBN: 0-471-49870-X
Page 1 and 2:
Organosilanes in Radical Chemistry
Page 3 and 4: DEDICATION To my parents XrZstoB an
Page 5 and 6: viii Contents 3.6 Hydrogen Atom: An
Page 7 and 8: PREFACE A large number of papers de
Page 9 and 10: ACKNOWLEDGEMENTS I thank Keith U. I
Page 11 and 12: 2 Formation and Structures of Silyl
Page 19 and 20: 10 Formation and Structures of Sily
Page 27 and 28: 2 Thermochemistry 2.1 GENERAL CONSI
Page 29 and 30: Bond Dissociation Enthalpies 21 Tab
Page 31 and 32: Bond Dissociation Enthalpies 23 2.2
Page 33 and 34: Ion Thermochemistry 25 Table 2.4 Re
Page 35 and 36: Ion Thermochemistry 27 Table 2.5 El
Page 37 and 38: References 29 3. Goumri, A., Yuan,
Page 39 and 40: 32 Hydrogen Donor Abilities of Sili
Page 53: 46 Hydrogen Donor Abilities of Sili
Page 57 and 58: General Aspects of Radical Chain Re
Page 59 and 60: Tris(trimethylsilyl)silane 53 Therm
Page 61 and 62: Tris(trimethylsilyl)silane 55 4.3.1
Page 63 and 64: Tris(trimethylsilyl)silane 57 A goo
Page 65 and 66: Tris(trimethylsilyl)silane 59 C(O)C
Page 67 and 68: Tris(trimethylsilyl)silane 61 radic
Page 69 and 70: Tris(trimethylsilyl)silane 63 86% y
Page 71 and 72: Tris(trimethylsilyl)silane 65 RO RO
Page 73 and 74: Tris(trimethylsilyl)silane 67 O AcO
Page 75 and 76: Tris(trimethylsilyl)silane 69 Tris(
Page 77 and 78: Other Silicon Hydrides 71 The reduc
Page 79 and 80: Other Silicon Hydrides 73 The decre
Page 81 and 82: Other Silicon Hydrides 75 Ph MeS O
Page 83 and 84: Other Silicon Hydrides 77 Table 4.6
Page 85 and 86: Silicon Hydride / Thiol Mixture 79
Page 87 and 88: Silylated Cyclohexadienes 81 and (4
Page 89 and 90: References 83 34. Kawashima, E., Uc
Page 91 and 92: References 85 104. Gimisis, T., Bal
Page 93 and 94: 88 Addition to Unsaturated Bonds te
Page 95 and 96: 90 Addition to Unsaturated Bonds ap
Page 97 and 98: 92 Addition to Unsaturated Bonds 5.
Page 99 and 100: 94 Addition to Unsaturated Bonds R
Page 101 and 102: 96 Addition to Unsaturated Bonds Ph
Page 103 and 104: 98 Addition to Unsaturated Bonds EP
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100 Addition to Unsaturated Bonds 5
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102 Addition to Unsaturated Bonds T
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104 Addition to Unsaturated Bonds R
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106 Addition to Unsaturated Bonds a
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110 Addition to Unsaturated Bonds S
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112 Addition to Unsaturated Bonds T
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114 Addition to Unsaturated Bonds I
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Page 123 and 124:
Page 125 and 126:
120 Unimolecular Reactions 1 Si(H)M
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122 Unimolecular Reactions t-Bu t-B
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124 Unimolecular Reactions MeO Si O
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126 Unimolecular Reactions t-Bu t-B
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128 Unimolecular Reactions R 1 R 2
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130 Unimolecular Reactions From the
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132 Unimolecular Reactions rearrang
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134 Unimolecular Reactions H 3 C +
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136 Unimolecular Reactions Br O Si(
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138 Unimolecular Reactions R3Si C C
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140 Unimolecular Reactions Me3Si O
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142 Unimolecular Reactions 43. Albe
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144 Consecutive Radical Reactions c
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146 Consecutive Radical Reactions O
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148 Consecutive Radical Reactions a
Page 155 and 156:
150 Consecutive Radical Reactions d
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152 Consecutive Radical Reactions T
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154 Consecutive Radical Reactions M
Page 161 and 162:
156 Consecutive Radical Reactions F
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Page 165 and 166:
Page 167 and 168:
162 Consecutive Radical Reactions i
Page 169 and 170:
164 Consecutive Radical Reactions A
Page 171 and 172:
Page 173 and 174:
168 Consecutive Radical Reactions r
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170 Consecutive Radical Reactions E
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Page 179 and 180:
174 Consecutive Radical Reactions A
Page 181 and 182:
176 Consecutive Radical Reactions P
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178 Consecutive Radical Reactions f
Page 185 and 186:
Page 187 and 188:
182 Consecutive Radical Reactions 1
Page 189 and 190:
184 Consecutive Radical Reactions 8
Page 191 and 192:
186 Silyl Radicals in Polymers and
Page 193 and 194:
Page 195 and 196:
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Page 213 and 214:
Page 215 and 216:
Page 217 and 218:
Page 219 and 220:
Page 221 and 222:
Page 223 and 224:
Page 225 and 226:
220 List of Abbreviations PED photo
Page 227 and 228:
222 Index Carbonyl sulfide 111 Carb
Page 229 and 230:
224 Index Organosilicon boranes 2,
Page 231 and 232:
226 Index Triethylsilane as mediato
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