1 The Chemistry of Ruthenium Oxidation Complexes ............... 1
1.1 Overview and Introduction ............................... 1
1.1.1 Discovery of Ruthenium ........................... 3
1.1.2 Oxidation States in Ruthenium Complexes .......... 3
1.1.3 Reviews on Ruthenium Complexes in Oxidation
Reactions ........................................ 4
1.1.4 Reviews on Oxidations of Organic Substrates
by Ru Complexes .................................. 4
1.1.5 Syntheses of Natural Products or
Pharmaceuticals by Ru Catalysts .................. 5
1.2 Ru(VIII) Complexes ...................................... 7
1.2.1 Ruthenium Tetroxide, RuO4 ........................ 7
1.2.2 Preparation ...................................... 7
1.2.3 Physical Properties .............................. 8
1.2.4 Analysis and Toxicity ........................... 10
1.2.5 RuO4 as an Organic Oxidant ...................... 11
1.2.6 Co-oxidants and Solvents for RuO4 Oxidations .... 12
1.2.7 Oxidations Effected by RuO4 ..................... 14
1.2.8 Other Ru(VIII) Complexes ........................ 30
1.3 Ru(VII) Complexes ...................................... 30
1.3.1 Perruthenates, TPAP and [RuO4]- ................. 30
1.3.2 Preparation ..................................... 31
1.3.3 Physical Properties ............................. 32
1.3.4 TPAP and [RuO4]- as Organic Oxidants ............ 33
1.3.5 Other Ru(VII) Species ........................... 40
1.4 Ru(VI) Complexes ....................................... 40
1.4.1 Ruthenates [RuO4]2- .............................. 41
1.4.2 Ru(VI) Complexes Containing Dioxo Moieties ...... 47
1.4.3 Ru(VI) Complexes Containing Mono-Oxo or
Nitride Donors .................................. 66
1.5 Ru(V) Complexes ........................................ 67
1.6 Ru(IV) Complexes ....................................... 69
1.6.1 Ruthenium Dioxide, RuO2 and RuO2.nH2O ............ 70
1.6.2 Ru(IV) Complexes with O- or N-Donors ............ 71
1.7 Ru(III) Complexes ...................................... 76
1.7.1 Ru(III) Complexes with O-Donors ................. 76
1.7.2 Ruthenium Trichloride, RuCL3, and RuCl3.nH2O ..... 79
1.7.3 RuBr3 and Halo-Aqua Complexes ................... 83
1.7.4 Ru(III) Complexes with Chelating O-, N-Donors ... 83
1.7.5 Ru(III) Complexes with N-Donors ................. 85
1.7.6 Ru(III) Complexes with -P, -As, -Sb and -S
Donors .......................................... 88
1.8 Ru(II-III) Complexes ................................... 89
1.9 Ru(II) Complexes ....................................... 89
1.9.1 Ru(II) Complexes with O- and N-Donors ........... 90
1.9.2 Ru(II) Complexes with Porphyrin,
Phthalocyanine and Macrocyclic Donors ........... 95
1.9.3 Ru(II) complexes with -P,-As and -Sb Donors ..... 97
1.9.4 Ru(II) Complexes with -S and -O Donors ......... 105
1.9.5 Ru(II) Complexes with -C Donors ................ 108
1.10 Ru(0) Complexes ....................................... 110
1.11 Appendix: Brief Resume of Preparations of Ru
Oxidants and Oxidation Reactions ...................... 110
1.11.1 Preparations of RuO4 In Situ for Oxidations ... 110
1.11.2 Preparations and Use of [RuO4]- ................ 111
1.11.3 Preparations and Use of [RuO4]2- ............... 112
1.11.4 Preparation of trans-Ru(O)2(bpy)
{I03(OH)3}1.5H2O ............................... 113
References ................................................. 113
2 Oxidation of Alcohols, Carbohydrates and Diols ............. 135
2.1 Primary Alcohols to Aldehydes (Table 2.1) ............. 136
2.1.1 Model Substrates ............................... 137
2.1.2 Specific Examples .............................. 137
2.1.3 Natural Product/Pharmaceutical Syntheses
Involving Primary Alcohol Oxidations ........... 139
2.2 Primary Alcohols to Carboxylic Acids (Table 2.1) ...... 141
2.2.1 Model Substrates ............................... 141
2.3 Secondary Alcohols to Ketones or Lactones ............. 142
2.3.1 Model Substrates ............................... 142
2.3.2 Specific Examples .............................. 145
2.3.3 Natural Product/Pharmaceutical Syntheses
Involving Secondary Alcohol Oxidations ......... 146
2.3.4 Hydroxylactones, α-Hydroxy Esters and
Cyanohydrins ................................... 148
2.3.5 Deracemisation of Secondary Alcohols ........... 148
2.3.6 Alcohols, Carbohydrates and Diols Not Covered
Here but Included in Chapter 1 ................. 149
2.3.7 Large-Scale Oxidations of Alcohols,
Carbohydrates and Diols ........................ 150
2.4 Carbohydrates ......................................... 151
2.4.1 Primary Alcohol Groups in Carbohydrates to
Carboxylic Acids ............................... 152
2.4.2 Secondary Alcohol Groups in Carbohydrates
to Ketones ..................................... 153
2.4.3 Syntheses of Carbohydrate Natural Products/
Pharmaceuticals ................................ 159
2.4.4 Miscellaneous Carbohydrate Oxidations .......... 160
2.5 Diols ................................................. 160
2.5.1 Specific Examples .............................. 160
2.5.2 Natural Product/Pharmaceutical Syntheses
Involving Diols ................................ 161
2.5.3 Desymmetrisation of Meso-Diols ................. 162
2.6 Miscellaneous Oxidations of Alcohols .................. 162
References ................................................. 163
3 Oxidation of Alkenes, Arenes and Alkynes ................... 173
3.1 Oxidation of Alkenes Involving No C=C Bond Cleavage ... 173
3.1.1 Epoxidation of Cyclic and Linear Alkenes ....... 174
3.1.2 Cis-Dihydroxylation of Alkenes ................. 181
3.1.3 Ketohydroxylations ............................. 185
3.2 Oxidative Cleavage of Alkenes ......................... 192
3.2.1 Alkene Cleavage to Aldehydes or Ketones ........ 192
3.2.2 Alkene Cleavage to Carboxylic Acids ............ 196
3.3 Oxidation of Arenes ................................... 200
3.3.1 Aromatic Rings to Carboxylic Acids or to CO2 ... 201
3.3.2 Phenols ........................................ 203
3.3.3 Polycyclic Arenes .............................. 203
3.3.4 Oxidative Coupling of Arenes and Napththols .... 204
3.3.5 Large-Scale Oxidations of Arenes ............... 204
3.3.6 Aromatic Substrates Not Covered Here but
Included in Chapter 1 .......................... 204
3.4 Oxidation of Alkynes .................................. 205
3.4.1 Oxidation of Alkynes Involving No C=C Bond
Cleavage ....................................... 205
3.4.2 Oxidative Cleavage of Alkynes to Carboxylic
Acids .......................................... 206
References ............................................ 207
4 Oxidation of Alkanes ....................................... 215
4.1 Oxidation of C-H Bonds in Alkanes ..................... 215
4.1.1 Aldehydes and Other R1R2R3CH Substrates ........ 215
4.1.2 Methylene Groups to Ketones .................... 216
4.1.3 Methyl Groups to Aldehydes or Carboxylic
Acids .......................................... 219
4.1.4 Cyclic Alkanes ................................. 219
4.1.5 Large-Scale Oxidations of Alkanes .............. 222
4.1.6 Alkane Oxidations Not Covered Here but
Included in Chapter 1 .......................... 222
4.2 Oxidation of C-C Bonds in Alkanes ..................... 223
References ............................................ 224
5 Oxidations of Amines, Amides, Ethers, Sulfides,
Phosphines, Arsines, Stibines and Miscellaneous
Substrates ................................................. 227
5.1 Oxidation of Amines ................................... 227
5.1.1 Primary Amines RCH2NH2 to Nitriles, Amides or
Ketones ........................................ 227
5.1.2 Secondary Amines, R1R2NH ....................... 229
5.1.3 Tertiary Amines R1R2R3N ......................... 231
5.1.4 Large-Scale Oxidation of Amines ................ 233
5.1.5 Amine Oxidations Not Covered Here but
Included in Chapter 1 .......................... 234
5.2 Oxidation of Amides ................................... 234
5.2.1 Cyclic α-Amino Acid Esters ..................... 234
5.2.2 N-Alkyllactams; β-Lactams to Acyloxy-β-
Lactams ........................................ 235
5.2.3 Substituted Pyrrolidines ....................... 235
5.2.4 Miscellaneous Amides ........................... 237
5.3 Oxidation of Ethers, R1R2O ............................ 238
5.3.1 Ethers to Esters ............................... 238
5.3.2 Ethers to Lactones ............................. 240
5.3.3 Other Ether Oxidations ......................... 240
5.3.4 Ether Oxidations Not Covered Here but
Included in Chapter 1 .......................... 241
5.4 Oxidation of Sulfides (thioethers), R1R2S ............. 241
5.4.1 Sulfides to Sulfoxides ......................... 241
5.4.2 Sulfides to Sulfones ........................... 242
5.4.3 Sulfoxides to Sulfones ......................... 243
5.4.4 Sulfides to Sulfates; Cyclic Sulfites to
Sulfates ....................................... 243
5.4.5 Sulfilimines to Sulfoximes;
N-Sulfonylsulfilimines to
N-Sulfonylsulfoximines ......................... 244
5.4.6 Asymmetric Epoxidations of Sulfides ............ 244
5.4.7 Large-Scale Oxidations of Sulfides and
Sulfites ....................................... 244
5.4.8 Sulfide Oxidations Not Covered Here but
Included in Chapter 1 .......................... 245
5.5 Oxidation of Phosphines, Arsines and Stibines ......... 245
5.5.1 Asymmetric Oxidations of Phosphines to
Phosphine Oxides ............................... 246
5.6 Oxidations of Miscellaneous Substrates ................ 246
5.6.1 Si-H Bonds in Organosilanes .................... 246
5.6.2 Nitriles ....................................... 246
5.6.3 Hydrocarbons in Coals .......................... 246
5.6.4 Nitro and Halide Compounds ..................... 247
5.6.5 Azidolactones; Depyrimidination of DNA ......... 247
5.6.6 Acids; Diones .................................. 248
5.6.7 Fullerenes ..................................... 248
References ............................................ 248
Index ......................................................... 253
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