Preface |
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xi | |
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Introduction to hydroformylation |
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1 | (14) |
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Piet W. N. M. van Leeuwen |
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History of phosphorus ligand effects |
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1 | (5) |
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6 | (2) |
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8 | (7) |
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Hydroformylation with unmodified rhodium catalysts |
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15 | (20) |
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15 | (1) |
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Regioselectivity in the rhodium-catalyzed hydroformylation of vinyl and vinylidenic substrates |
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16 | (6) |
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17 | (1) |
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Influence of the alkene structure on the regioselectivity |
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17 | (4) |
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21 | (1) |
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Influence of CO and H2 partial pressures |
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22 | (1) |
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Mechanism of the hydroformylation of vinyl and vinylidenic alkenes |
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22 | (7) |
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Activation of the catalyst precursor |
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24 | (1) |
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Behavior of the isomeric alkyl-metal intermediates via deuterioformylation |
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24 | (4) |
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In situ IR investigation of the formation and reactivity of acylrhodium intermediates |
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28 | (1) |
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Origin of the regioselectivity |
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29 | (6) |
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Influence of the nature of the substrate |
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29 | (2) |
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Influence of the reaction parameters |
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31 | (4) |
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Rhodium phosphite catalysts |
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35 | (28) |
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Piet W. N. M. van Leeuwen |
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35 | (2) |
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37 | (7) |
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37 | (3) |
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Mechanistic and kinetic studies |
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40 | (4) |
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44 | (11) |
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44 | (4) |
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Mechanistic and kinetic studies |
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48 | (7) |
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Hydroformylation of internal alkenes |
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55 | (4) |
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Hydroformylation of less reactive internal and functionalized alkenes |
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55 | (2) |
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Formation of linear aldehydes starting from internal alkenes |
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57 | (2) |
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Calixarene based phosphites |
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59 | (4) |
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63 | (44) |
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Piet W. N. M. van Leeuwen |
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Monophosphines as ligands |
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63 | (13) |
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63 | (1) |
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64 | (2) |
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66 | (2) |
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68 | (1) |
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69 | (3) |
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72 | (3) |
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75 | (1) |
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76 | (31) |
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76 | (2) |
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Ferrocene based diphosphine ligands |
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78 | (4) |
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BISBI ligands and the natural bite angle |
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82 | (5) |
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Xantphos ligands: tunable bite angles |
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87 | (9) |
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The mechanism, regioselectivity, and the bite angle. Concluding remarks |
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96 | (11) |
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Asymmetric hydroformylation |
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107 | (38) |
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107 | (2) |
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Rhodium systems with chiral diphosphite ligands |
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109 | (15) |
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C2 Symmetric chiral diphosphite ligands |
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109 | (2) |
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Catalyst preparation and hydroformylation |
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111 | (2) |
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Characterisation of RhH(L)(CO)2 intermediates. Solution structures of hydroformylation catalysts |
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113 | (2) |
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Structure versus stability and enantioselectivity |
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115 | (1) |
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Chiral cooperativity and effect of substituents in diastereomeric diphosphite ligands |
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116 | (5) |
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C1 Sugar backbone derivatives. Diphosphinite and diphosphite ligands |
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121 | (3) |
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Phosphine-phosphite rhodium catalysts |
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124 | (7) |
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124 | (1) |
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Rhodium complexes with BINAPHOS and related ligands |
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124 | (3) |
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RhH(CO)2(BINAPHOS) complexes; models for enantioselectivity |
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127 | (2) |
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Separation studies for the BINAPHOS system |
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129 | (1) |
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Chiral phosphine-phosphite ligands containing a stereocenter in the backbone |
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129 | (2) |
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Diphosphine rhodium catalysts |
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131 | (7) |
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131 | (1) |
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C1 Diphosphines as chiral ligands |
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131 | (1) |
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C2 Diphosphines as chiral ligands |
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132 | (4) |
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The Rh/BDPP system. HPNMR and HPIR studies under hydroformylation conditions |
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136 | (2) |
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Mechanistic considerations |
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138 | (7) |
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138 | (2) |
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Enantioselectivity and conclusions |
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140 | (5) |
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Hydroformylation in organic synthesis |
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145 | (44) |
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145 | (1) |
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Hydroformylation of unfunctionalized alkenes |
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146 | (3) |
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Hydroformylation of functionalized alkenes |
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149 | (6) |
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Substrate directed stereoselectivity |
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155 | (5) |
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Control of the regio- and stereoselectivity by heteroatomdirected hydroformylation |
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160 | (4) |
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Consecutive processes under hydroformylation conditions |
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164 | (14) |
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Hydroformylation-acetalization (intramolecular) |
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165 | (1) |
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Hydroformylation-acetalization (intermolecular) |
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166 | (2) |
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Hydroformylation-amination (intramolecular) |
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168 | (4) |
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Hydroformylation-amination-reduction. Hydroaminomethylation |
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172 | (3) |
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Consecutive hydroformylation-aldol reaction |
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175 | (2) |
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Consecutive hydroformylation-Wittig reaction |
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177 | (1) |
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178 | (4) |
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182 | (7) |
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Aqueous biphasic hydroformylation |
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189 | (14) |
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Principles of biphasic reactions in water |
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189 | (2) |
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Why two-phase catalysis? Scope and Limitations |
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189 | (1) |
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Concepts for two-phase hydroformylation |
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190 | (1) |
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Hydroformylation of propene and butene |
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191 | (8) |
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Historic overview of two-phase hydroformylation technology |
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191 | (1) |
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191 | (2) |
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Kinetics and catalyst pre-formation |
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193 | (3) |
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196 | (1) |
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Status of the operated plants |
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197 | (1) |
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198 | (1) |
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Reaction of various alkenes |
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199 | (4) |
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Ethylene to propanal: why not applied? |
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199 | (1) |
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200 | (3) |
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Process aspects of rhodium-catalyzed hydroformylation |
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203 | (30) |
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203 | (1) |
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204 | (2) |
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Catalyst selectivity and activity |
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206 | (2) |
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206 | (1) |
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207 | (1) |
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Catalyst stability; degradation routes, losses and recovery |
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208 | (3) |
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208 | (1) |
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209 | (1) |
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Catalyst recovery processes |
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210 | (1) |
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211 | (9) |
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Type I: Stripping reactor process/Rh containment in reactor |
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212 | (1) |
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Type II: Liquid recycle process/use of distillative separation |
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213 | (2) |
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Type III: Two-phase reaction/extraction process |
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215 | (1) |
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Type IV: Extraction after one-phase reaction |
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216 | (4) |
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Survey of commercialized processes and new developments |
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220 | (13) |
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Hydroformylation of butenes |
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220 | (3) |
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Branched higher alkenes to mainly plasticizer alcohols |
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223 | (1) |
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Linear higher alkenes to mainly detergent alcohols |
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223 | (2) |
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225 | (1) |
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226 | (7) |
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Catalyst preparation and decomposition |
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233 | (20) |
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Piet W. N. M. van Leeuwen |
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233 | (1) |
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233 | (2) |
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235 | (14) |
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Metal plating or cluster formation |
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235 | (1) |
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Oxidation of phosphorus ligands |
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235 | (2) |
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Phosphorus-carbon bond breaking in phosphines |
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237 | (6) |
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Decomposition of phosphites |
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243 | (4) |
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Formation of dormant sites |
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247 | (2) |
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249 | (4) |
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Novel developments in hydroformylation |
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253 | (28) |
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Piet W. N. M. van Leeuwen |
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253 | (1) |
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253 | (3) |
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Novel developments in catalyst separation |
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256 | (18) |
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256 | (4) |
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Supported aqueous phase catalysis (SAPC) |
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260 | (2) |
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Hydroformylation in supercritical fluids |
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262 | (3) |
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Fluorous Biphase catalysis |
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265 | (2) |
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Dendrimer supported catalysts |
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267 | (2) |
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Novel developments in polymer supported catalyst |
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269 | (5) |
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274 | (3) |
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277 | (4) |
Subject index |
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281 | |