Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 38 (eBook)

Science of Synthesis – Volume 38: Peroxides 1
Title page 3
Imprint 5
Preface 6
Overview 8
Table of Contents 10
Introduction 28
38.1 Product Class 1: Alkyl and Cycloalkyl Hydroperoxides 36
38.1.1 Product Subclass 1: a-Unsubstituted Alkyl Hydroperoxides 36
38.1.1.1 Synthesis of Product Subclass 1 37
38.1.1.1.1 Method 1: Reactions of Alkanes with Molecular Oxygen 37
38.1.1.1.2 Method 2: Hydrolysis of Alkyl Metal and Alkyl Metalloid Peroxides 38
38.1.1.1.2.1 Variation 1: Via Oxidation of Alkylmagnesium Halides with Molecular Oxygen 38
38.1.1.1.2.2 Variation 2: Via Oxidation of Alkylboron Halides with Molecular Oxygen 39
38.1.1.1.3 Method 3: Reaction of Oxetanes with Hydrogen Peroxide 40
38.1.1.1.4 Method 4: Reaction of Epoxides with Hydrogen Peroxide 41
38.1.1.1.4.1 Variation 1: Catalyzed by Methyltrioctylammonium Tetrakis(oxodiperoxotungsto)phosphate 42
38.1.1.1.5 Method 5: Reaction of Alkyl Halides 43
38.1.1.1.5.1 Variation 1: With Hydrogen Peroxide in the Presence of Silver(I) Trifluoroacetate 43
38.1.1.1.5.2 Variation 2: With 2-Alkoxypropan-2-yl and 2-(2-Methoxyethoxy)propan-2-yl Hydroperoxides 44
38.1.1.1.5.3 Variation 3: With Potassium Superoxide 45
38.1.1.1.6 Method 6: Reaction of Alcohols with Hydrogen Peroxide 46
38.1.1.1.6.1 Variation 1: Without Catalysts 46
38.1.1.1.6.2 Variation 2: With Acid Catalysis 47
38.1.1.1.7 Method 7: Reaction of Dialkyl Sulfates with Hydrogen Peroxide 47
38.1.1.1.8 Method 8: Reaction of Alkyl Methanesulfonates with Hydrogen Peroxide 48
38.1.1.1.8.1 Variation 1: Reaction of Homoallylic Methanesulfonates with Hydrogen Peroxide 49
38.1.1.1.8.2 Variation 2: Reaction of Cyclic Homoallylic 4-Bromobenzenesulfonates with Hydrogen Peroxide 50
38.1.1.1.9 Method 9: Reaction of 1-Substituted 1-Sulfonylhydrazines with Molecular Oxygen under Basic Conditions 50
38.1.1.1.10 Method 10: Reaction of 1-Alkyl-2-tosylhydrazines with Hydrogen Peroxide and Sodium Peroxide 51
38.1.1.1.11 Method 11: Synthesis from Alkenes 52
38.1.1.1.11.1 Variation 1: With Triethylsilane and Oxygen with a Cobalt(II) Catalyst 53
38.1.1.1.11.2 Variation 2: Photooxygenation with Methylene Blue Sensitizer 54
38.1.1.1.11.3 Variation 3: Photooxygenation with 4-Chlorobenzenethiol 55
38.1.1.1.11.4 Variation 4: With N-Bromosuccinimide and Hydrogen Peroxide 55
38.1.1.1.11.5 Variation 5: With 1,3-Dibromo-5,5-dimethylhydantoin and Hydrogen Peroxide 56
38.1.1.1.12 Method 12: Synthesis from Conjugated Dienes 57
38.1.1.1.13 Method 13: Synthesis from Peroxy Esters 57
38.1.1.2 Applications of Product Subclass 1 in Organic Synthesis 58
38.1.2 Product Subclass 2: a-Halogen-Substituted Alkyl Hydroperoxides 58
38.1.2.1 Synthesis of Product Subclass 2 59
38.1.2.1.1 a-Fluoroalkyl Hydroperoxides 59
38.1.2.1.1.1 Method 1: Decomposition of Hexafluoroacetone Perhydrate 59
38.1.2.1.1.2 Method 2: Reaction of Perfluoroperoxy Derivatives with Water 59
38.1.2.1.2 a-Chloroalkyl Hydroperoxides 60
38.1.2.1.2.1 Method 1: Reaction of Chloroalkenes with Ozone 60
38.1.3 Product Subclass 3: a-Oxygen-Substituted Alkyl Hydroperoxides 61
38.1.3.1 Synthesis of Product Subclass 3 61
38.1.3.1.1 a-Hydroxyalkyl Hydroperoxides 61
38.1.3.1.1.1 Method 1: Reaction of Aldehydes with Hydrogen Peroxide and Iodine 61
38.1.3.1.1.2 Method 2: Reaction of a-Halo Ketones with Hydrogen Peroxide 62
38.1.3.1.2 a-Alkoxyalkyl Hydroperoxides 63
38.1.3.1.2.1 Method 1: Ozonolysis of Alkenes 63
38.1.3.1.2.2 Method 2: Reaction of Vinyl Ethers with Ozone and Alcohols 65
38.1.3.1.2.2.1 Variation 1: With Hydrogen Peroxide 67
38.1.3.1.2.2.2 Variation 2: With Hydrogen Peroxide and Silica Gel 67
38.1.3.1.2.2.3 Variation 3: With Hydrogen Peroxide and Molybdenum(VI) Oxide 68
38.1.3.1.2.3 Method 3: Reaction of Dialkyl Ethers with Molecular Oxygen 69
38.1.3.1.2.4 Method 4: a-Reaction of Cyclopropyl Alcohols with Hydrogen Peroxide 69
38.1.3.1.2.5 Method 5: Reaction of Ketones and Alcohols with Hydrogen Peroxide 71
38.1.3.1.2.6 Method 6: Reaction of Hydroxy Ketones and Diketones with Hydrogen Peroxide 71
38.1.3.1.2.7 Method 7: Reaction of Ketones with Hydrogen Peroxide Catalyzed by Iodine 72
38.1.3.1.2.8 Method 8: Reaction of Homoallylic 4-Bromobenzenesulfonates and Hydrogen Peroxide 73
38.1.3.1.2.9 Method 9: Ring Opening of Oxetanes with Hydrogen Peroxide 74
38.1.3.1.3 a-Peroxyalkyl Hydroperoxides 74
38.1.3.1.3.1 Method 1: Reaction of Alkenes and Vinyl Ethers with Ozone 74
38.1.3.1.3.1.1 Variation 1: Intramolecular Reaction of Alkyl Hydroperoxides with Carbonyl Oxides Generated by Ozonolysis of Alkenes 75
38.1.3.1.3.2 Method 2: Reaction of Ketones with Hydrogen Peroxide 76
38.1.3.1.3.3 Method 3: Reaction of Acetals with Hydrogen Peroxide Mediated by Boron Trifluoride--Diethyl Ether Complex 76
38.1.3.1.3.4 Method 4: Reaction of Dialkyl Ethers with Molecular Oxygen 77
38.1.3.1.4 a-(Triorganosiloxy)alkyl Hydroperoxides 78
38.1.3.1.4.1 Method 1: Reaction of Trialkylsilyl Vinyl Ethers and Hydrogen Peroxide 78
38.1.3.1.5 a-(Acyloxy)alkyl Hydroperoxides 78
38.1.3.1.5.1 Method 1: Photooxidation of an Enol Lactone 78
38.1.3.1.6 1,1-Bis(hydroperoxy)alkanes 79
38.1.3.1.6.1 Method 1: Reaction of Ketones with Hydrogen Peroxide with Acid Catalysts 79
38.1.3.1.6.1.1 Variation 1: With 1,2-Bis(diphenylphosphoryl)ethane 80
38.1.3.1.6.1.2 Variation 2: Catalyzed by Ammonium Cerium(IV) Nitrate 81
38.1.3.1.6.1.3 Variation 3: Catalyzed by Methyltrioxorhenium(VII) in Trifluoroethanol 82
38.1.3.1.6.1.4 Variation 4: Catalyzed by Molecular Iodine 82
38.1.3.1.6.1.5 Variation 5: Catalyzed by Tungstic Acid 83
38.1.3.1.6.2 Method 2: Reaction of Tosylhydrazones with Hydrogen Peroxide 84
38.1.3.1.6.3 Method 3: Reaction of Vinyl Ethers with Ozone and Hydrogen Peroxide 85
38.1.3.1.6.4 Method 4: Reaction of Ketals with Hydrogen Peroxide 86
38.1.3.1.6.5 Method 5: Ring Opening of Bicyclic Benzyl Alcohols with Hydrogen Peroxide 87
38.1.3.2 Applications of Product Subclass 3 in Organic Synthesis 87
38.1.4 Product Subclass 4: a-Sulfur-Substituted Alkyl Hydroperoxides 88
38.1.4.1 Synthesis of Product Subclass 4 88
38.1.4.1.1 Method 1: Photooxidation of Thiazolidines with Molecular Oxygen in the Presence of Tetraphenylphorphyrin 88
38.1.5 Product Subclass 5: a-Nitrogen-Substituted Alkyl Hydroperoxides 88
38.1.5.1 Synthesis of Product Subclass 5 89
38.1.5.1.1 a-Aminoalkyl Hydroperoxides 89
38.1.5.1.1.1 Method 1: Reaction of Carbonyl Compounds with Ammonia or Amines and Hydrogen Peroxide 89
38.1.5.1.2 a-(Acylamino)alkyl Hydroperoxides 91
38.1.5.1.2.1 Method 1: Reaction of Cyclic Amides and N-Alkylamides with Oxygen 91
38.1.5.1.2.2 Method 2: Reaction of N-Heterocycles with Hydrogen Peroxide 91
38.1.5.1.3 a-Hydrazinoalkyl Hydroperoxides 92
38.1.5.1.3.1 Method 1: Oxidation of Hydrazoalkanes 92
38.1.5.1.4 a-(N-Alkyl-N-nitrosoamino)alkyl Hydroperoxides 92
38.1.5.1.4.1 Method 1: Reaction of Dialkylnitrosamines with Lithium Diisopropylamide and Oxygen 92
38.1.5.1.4.2 Method 2: Reaction of 1-Acetoxyalkyl(alkyl)nitrosamines with Hydrogen Peroxide 93
38.1.5.1.5 4-Hydroperoxy-1,3,2-oxazaphosphorinane 2-Oxides 94
38.1.5.1.5.1 Method 1: Reaction of 4-Hydroxy-1,3,2-oxazaphosphorinane 2-Oxides with Hydrogen Peroxide 94
38.1.5.1.5.2 Method 2: Reaction of a Phosphoric Amide Diester Bearing O- or N-Alkenyl Residues and Ozone 94
38.1.5.2 Applications of Product Subclass 5 in Organic Synthesis 95
38.2 Product Class 2: Allylic Hydroperoxides 100
38.2.1 Synthesis of Product Class 2 105
38.2.1.1 Method 1: Synthesis from Alkenes 105
38.2.1.1.1 Variation 1: With Triplet Dioxygen 105
38.2.1.1.2 Variation 2: With Singlet Dioxygen 107
38.2.1.2 Method 2: Synthesis from Arenes 120
38.2.1.2.1 Variation 1: Reaction with Dioxygen under Basic Conditions 120
38.2.1.2.2 Variation 2: Reaction with Triplet Dioxygen in the Presence of Transition Metal Compounds 122
38.2.1.2.3 Variation 3: Reaction with Singlet Dioxygen 123
38.2.1.3 Method 3: Synthesis from Allylic Halides 125
38.2.1.3.1 Variation 1: Reaction with Hydrogen Peroxide 125
38.2.1.4 Method 4: Synthesis from Allyl Sulfonates 126
38.2.1.4.1 Variation 1: Reaction with Hydrogen Peroxide 126
38.2.1.5 Method 5: Synthesis from Endoperoxides 127
38.2.1.5.1 Variation 1: Reaction with Nucleophiles 127
38.2.1.6 Method 6: Synthesis from Allyl Hydroperoxides 128
38.2.1.6.1 Variation 1: Via Rearrangement 128
38.2.1.6.2 Variation 2: Separation of Racemates via HPLC 129
38.2.1.6.3 Variation 3: Enzymatic Kinetic Resolution of Racemates 130
38.3 Product Class 3: Benzylic Hydroperoxides 136
38.3.1 Synthesis of Product Class 3 137
38.3.1.1 Method 1: Synthesis from Aryl- or Hetarylalkanes with Retention of the Carbon Skeleton 139
38.3.1.1.1 Variation 1: Autoxidation 139
38.3.1.1.2 Variation 2: Reaction with Dioxygen in the Presence of Metal Ions 144
38.3.1.1.3 Variation 3: Reaction with Dioxygen in the Presence of Bases 145
38.3.1.1.4 Variation 4: Reaction with Dioxygen in the Presence of N-Hydroxyphthalimide 146
38.3.1.1.5 Variation 5: Reaction with tert-Butyl Hydroperoxide and a Transition-Metal Catalyst 146
38.3.1.1.6 Variation 6: Reaction with Dioxygen in the Presence of Photochemically Excited Electron-Transfer Reagents 147
38.3.1.2 Method 2: Synthesis from Arylalkanes in Combination with C--C Bond Cleavage 148
38.3.1.2.1 Variation 1: Photochemically Induced Reaction 148
38.3.1.3 Method 3: Synthesis from Alkenes 149
38.3.1.3.1 Variation 1: With Triplet Dioxygen in the Presence of Thiols 149
38.3.1.3.2 Variation 2: Reaction with Triplet Dioxygen in the Presence of Cobalt(II) Compounds and Silanes 149
38.3.1.3.3 Variation 3: Reaction with Triplet Dioxygen and Boranes 150
38.3.1.3.4 Variation 4: Via Electron-Transfer Processes 151
38.3.1.3.5 Variation 5: Reaction with Singlet Dioxygen 152
38.3.1.3.6 Variation 6: Reaction with Hydrogen Peroxide and Mercury(II) Salts 152
38.3.1.4 Method 4: Synthesis from Arenes 153
38.3.1.4.1 Variation 1: From Phenols with Dioxygen in the Absence of Catalysts 153
38.3.1.4.2 Variation 2: Reaction with Singlet Dioxygen 155
38.3.1.5 Method 5: Synthesis from Haloalkanes 156
38.3.1.5.1 Variation 1: With Hydrogen Peroxide under Acidic Conditions 156
38.3.1.5.2 Variation 2: With Hydrogen Peroxide under Basic Conditions 157
38.3.1.6 Method 6: Synthesis from Alcohols 157
38.3.1.6.1 Variation 1: By Reaction with Hydrogen Peroxide under Acidic Conditions 157
38.3.1.7 Method 7: Synthesis from Carboxylic Acid Esters 158
38.3.1.7.1 Variation 1: Reaction with Hydrogen Peroxide 158
38.3.1.8 Method 8: Synthesis from Ethers 159
38.3.1.8.1 Variation 1: Reaction of Acyclic Ethers with Hydrogen Peroxide 159
38.3.1.9 Method 9: Synthesis from Peroxy Esters 160
38.3.1.9.1 Variation 1: Hydrolysis in the Presence of Bis(tributyltin) Oxide 160
38.3.1.10 Method 10: Synthesis from Other Benzylic Hydroperoxides 160
38.3.1.10.1 Variation 1: Separation of Racemates via HPLC 160
38.3.1.10.2 Variation 2: Kinetic Resolution of Racemates Using Enantiopure Phosphines 161
38.3.1.10.3 Variation 3: Lipase-Catalyzed Kinetic Resolution of Racemates 161
38.3.1.10.4 Variation 4: Kinetic Resolution of Racemates Using Native Peroxidases 162
38.3.1.10.5 Variation 5: Enzymatic Kinetic Resolution of Racemates Using a Semisynthetic Peroxidase 164
38.3.1.10.6 Variation 6: Kinetic Resolution of Racemates Using Microorganisms 165
38.4 Product Class 4: Salts of Alkyl Hydroperoxides 170
38.4.1 Product Subclass 1: Group 15 Salts of Alkyl Hydroperoxides 171
38.4.1.1 Synthesis of Product Subclass 1 171
38.4.1.1.1 Method 1: Synthesis of (Alkylperoxy)antimony Compounds 171
38.4.2 Product Subclass 2: Group 14 Salts of Alkyl Hydroperoxides 171
38.4.2.1 Synthesis of Product Subclass 2 172
38.4.2.1.1 Method 1: Synthesis of (Alkylperoxy)silanes 172
38.4.2.1.1.1 Variation 1: Reaction of Silyl Enol Ethers with Singlet Oxygen 172
38.4.2.1.1.2 Variation 2: Reaction of Chlorotriorganosilanes or Triorganosilyl Trifluoromethanesulfonates with Alkyl Hydroperoxides 173
38.4.2.1.1.3 Variation 3: Reaction of N,O-Bis(triorganosilyl)acetamides with Alkyl Hydroperoxides 177
38.4.2.1.1.4 Variation 4: Reaction of .-Silyl Allylic Alcohols with Ozone 177
38.4.2.1.1.5 Variation 5: Reaction of Alkenes with Oxygen and Triethylsilane Promoted by Cobalt(II) Catalysts 178
38.4.2.1.2 Method 2: Synthesis of Germanium Alkyl Peroxides 180
38.4.2.1.2.1 Variation 1: Reaction of Halogermanes with Alkyl Hydroperoxides and Ammonia or Tertiary Amines 180
38.4.2.1.3 Method 3: Synthesis of Tin Alkyl Peroxides 181
38.4.2.1.3.1 Variation 1: Reaction of Triorganostannanes with Alkyl Hydroperoxides 181
38.4.2.1.3.2 Variation 2: Reaction of Hydroxytriorganostannanes or Oxytriorganostannanes with Alkyl Hydroperoxides 181
38.4.2.1.3.3 Variation 3: Synthesis of 1,3-Bis(alkylperoxy)-1,1,3,3-tetraorganodistannoxanes and (Alkylperoxy)(chloro)-1,1,3,3-tetraorganodistannoxanes 182
38.4.3 Product Subclass 3: Group 13 Salts of Alkyl Hydroperoxides 183
38.4.3.1 Synthesis of Product Subclass 3 183
38.4.3.1.1 Method 1: Synthesis of (Alkylperoxy)boron Compounds 183
38.4.3.1.1.1 Variation 1: Reaction of Trialkylboranes with Oxygen 183
38.4.3.1.1.2 Variation 2: Reaction of Boron Halides with Alkyl Hydroperoxides 185
38.4.3.1.1.3 Variation 3: Reaction of Tetraacetyl Diborate with Alkyl Hydroperoxides 185
38.4.3.1.1.4 Variation 4: Reaction of Alkyldichloroboranes or Chlorodicyclopentylborane with Molecular Oxygen 186
38.4.3.1.1.5 Variation 5: Oxidation of Trialkylboroxins 186
38.4.3.1.2 Method 2: Synthesis of Aluminum Alkyl Peroxides 187
38.4.3.1.3 Method 3: Synthesis of Indium Alkyl Peroxides 187
38.4.4 Product Subclass 4: Group 2 Salts of Alkyl Hydroperoxides 188
38.4.4.1 Synthesis of Product Subclass 4 188
38.4.4.1.1 Method 1: Synthesis of Magnesium Alkyl Peroxides 188
38.4.4.1.1.1 Variation 1: Reaction of Organomagnesium Halides with Oxygen 188
38.4.4.1.2 Method 2: Synthesis of Strontium Alkyl Peroxides 189
38.4.4.1.3 Method 3: Synthesis of Barium Alkyl Peroxides 189
38.4.5 Product Subclass 5: Group 1 Salts of Alkyl Hydroperoxides 189
38.4.5.1 Synthesis of Product Subclass 5 189
38.4.5.1.1 Method 1: Synthesis of Lithium Alkyl Peroxides 190
38.4.5.1.2 Method 2: Synthesis of Sodium Alkyl Peroxides 190
38.4.5.1.2.1 Variation 1: Reaction of Sodium tert-Butoxide with Alkyl Hydroperoxides 190
38.4.5.1.3 Method 3: Synthesis of Potassium Alkyl Peroxides 190
38.4.6 Product Subclass 6: Transition Metal Salts of Alkyl Hydroperoxides 191
38.4.6.1 Synthesis of Product Subclass 6 191
38.4.6.1.1 Method 1: Synthesis of Zinc Alkyl Peroxides 191
38.4.6.1.2 Method 2: Synthesis of Cadmium Alkyl Peroxides 191
38.4.6.1.2.1 Variation 1: Reaction of Alkylcadmium(II) Compounds with Alkyl Hydroperoxides 192
38.4.6.1.3 Method 3: Synthesis of Mercury Alkyl Peroxides 192
38.4.6.1.4 Method 4: Synthesis of Palladium Alkyl Peroxides 193
38.4.6.1.4.1 Variation 1: Reaction of Palladium(II) Carboxylates with Alkyl Hydroperoxides 193
38.4.6.1.4.2 Variation 2: Reaction of an Alkyl(bisphosphine)(hydroxy)palladium(II) Complex with an Alkyl Hydroperoxide 193
38.4.6.1.4.3 Variation 3: Reaction of (Dioxygen)bis(triphenylphosphine)palladium(II) with Electron-Deficient Alkenes 194
38.4.6.1.5 Method 5: Synthesis of Platinum Alkyl Peroxides 194
38.4.6.1.5.1 Variation 1: Reaction of Hydroxy(organo)bis(triorganophosphine)platinum(II) Complexes with Alkyl Hydroperoxides 194
38.4.6.1.5.2 Variation 2: Reaction of (Dioxygen)bis(triphenylphosphine)platinum(II) Complexes with Electron-Deficient Alkenes 195
38.4.6.1.5.3 Variation 3: Reaction of (Dioxygen)bis(triphenylphosphine)platinum(II) Complexes with Carbonyl Compounds 196
38.4.6.1.6 Method 6: Synthesis of Cobalt Alkyl Peroxides 197
38.4.6.1.6.1 Variation 1: Reaction of Organocobaloximes with Oxygen 197
38.4.6.1.6.2 Variation 2: Reaction of Cobalt(II) Complexes with Alkyl Hydroperoxides 198
38.4.6.1.6.3 Variation 3: Reaction of Cobalt(II) Complexes with Oxygen and Phenols 198
38.4.6.1.6.4 Variation 4: Reaction of Cobalt(II) Superoxo Complexes with Phenoxyl Radicals 200
38.4.6.1.7 Method 7: Synthesis of Iridium Alkyl Peroxide 200
38.4.6.1.8 Method 8: Synthesis of Titanium and Zirconium Alkyl Peroxides 201
38.4.6.1.9 Method 9: Synthesis of Molybdenum and Tungsten Alkyl Peroxides 201
38.4.6.1.10 Method 10: Synthesis of Hafnium Alkyl Peroxides 202
38.4.6.1.11 Method 11: Synthesis of Vanadium Alkyl Peroxides 203
38.5 Product Class 5: Alkyl and Cycloalkyl Peroxides 206
38.5.1 Synthesis of Product Class 5 207
38.5.1.1 Method 1: Nucleophilic Substitution 207
38.5.1.1.1 Variation 1: Reaction of Alkyl Hydroperoxides with Alkyl Bromides or Methanesulfonates under Basic Conditions 207
38.5.1.1.2 Variation 2: Reaction of Alkyl Bromides or Sulfonates with Potassium Superoxide 209
38.5.1.1.3 Variation 3: Phase-Transfer-Catalyzed Synthesis of Primary--Tertiary Bisperoxides 210
38.5.1.1.4 Variation 4: Reaction between Germanium or Tin Peroxides and Alkyl Trifluoromethanesulfonates 211
38.5.1.1.5 Variation 5: Acid-Catalyzed Reaction of Alkyl Hydroperoxides with Tertiary Alkyl Trichloroacetimidates 212
38.5.1.1.6 Variation 6: Reaction of Alkyl Hydroperoxides with Alkyl Bromides in Ionic Liquids 214
38.5.1.1.7 Variation 7: 1,1-Bis(alkylperoxy)alkanes via Alkylation of 1,1-Bis(hydroperoxy)alkanes 214
38.5.1.2 Method 2: Addition to a Double Bond 217
38.5.1.2.1 Variation 1: Acid-Catalyzed Addition of Alkyl Hydroperoxides to Enol Ethers 217
38.5.1.2.2 Variation 2: Base-Catalyzed Addition of Alkyl Hydroperoxides to Electron-Deficient Alkenes 218
38.5.1.2.3 Variation 3: Peroxymercuration of Alkenes Followed by Bromodemercuration 219
38.5.1.2.4 Variation 4: Cobalt-Catalyzed Triethylsilylperoxidation of Alkenes with Molecular Oxygen 220
38.5.1.3 Method 3: Peroxycarbenium-Mediated C--C Bond Formation from Monoperoxyketals and Monoperoxyacetals 221
38.5.1.3.1 Variation 1: Allylation of Monoperoxyketals and Monoperoxyacetals 223
38.5.1.3.2 Variation 2: Crotylation of Monoperoxyacetals 224
38.5.1.3.3 Variation 3: Synthesis of 3-Peroxy Ketones 225
38.5.1.3.4 Variation 4: Synthesis of 3-Peroxy Esters 226
38.5.1.4 Method 4: Opening of Oxetanes with Alkyl Hydroperoxides 226
38.5.1.5 Method 5: Opening of Epoxides with Alkyl Hydroperoxides 227
38.5.1.6 Method 6: Ruthenium-Catalyzed Oxidation of Tertiary Amines with Alkyl Hydroperoxides 228
38.5.1.7 Method 7: Epoxy Alkyl Peroxides from Allylic Alcohols Bearing an Appropriately Positioned Lactam Ring 229
38.6 Product Class 6: Allylic Peroxides 232
38.6.1 Synthesis of Product Class 6 232
38.6.1.1 Method 1: Nucleophilic Substitution 232
38.6.1.1.1 Variation 1: Reaction of Allylic Bromides with Alkyl Hydroperoxides under Basic Conditions 232
38.6.1.1.2 Variation 2: Alkylation of Hydroperoxyacetals under Basic Conditions 233
38.6.1.1.3 Variation 3: Diallylation of 1,1-Bis(hydroperoxy)alkanes under Basic Conditions 234
38.6.1.1.4 Variation 4: Alkylation of Allylic Hydroperoxides with an Alkyl Halide or Sulfonate under Basic Conditions 235
38.6.1.1.5 Variation 5: Reaction of Allylic Alcohols with tert-Butyl Hydroperoxide under Acidic Conditions 235
38.6.1.1.6 Variation 6: Reaction of Allylic Alcohols with tert-Butyl Hydroperoxide Catalyzed by a Polyoxometalate 236
38.6.1.1.7 Variation 7: Reaction of Alkyl Hydroperoxides and Tertiary Alkyl Trichloroacetimidates under Acidic Conditions 237
38.6.1.2 Method 2: Synthesis of Allylic Peroxides via Tritylation and Methoxymethylation of Allylic Stannyl Peroxides 238
38.6.1.3 Method 3: Allylic Peroxyketals via the Acid-Catalyzed Addition of Allylic Hydroperoxides to Enol Ethers 239
38.6.1.4 Method 4: Allylic Peroxidation of Alkenes with tert-Butyl Hydroperoxide 240
38.6.1.4.1 Variation 1: Palladium-Catalyzed Allylic Peroxidation of Cycloalkenes 240
38.6.1.4.2 Variation 2: Palladium/Carbon-Catalyzed Allylic Peroxidation of 1,4-Dienes 241
38.6.1.4.3 Variation 3: Palladium(II) Hydroxide/Carbon Catalyzed Allylic Peroxidation of Enones 242
38.6.1.4.4 Variation 4: Allylic Peroxidation of Cyclohexene Catalyzed by Manganese(II), Cobalt(II), Nickel(II), Copper(II), and Vanadyl Complexes Supported on Alumina 242
38.6.1.4.5 Variation 5: Allylic Peroxidation of Cyclohexene Catalyzed by Molybdenum Oxide and Vanadium Oxide Clusters 244
38.6.1.4.6 Variation 6: Allylic Peroxidation of Cycloalkenes with tert-Butyl Hydroperoxide Catalyzed by Pyridinium Chlorochromate or Pyridinium Dichromate 245
38.6.1.5 Method 5: Reaction of Conjugated Dienes and Trienes with Pyridinium Dichromate and tert-Butyl Hydroperoxide 245
38.6.1.6 Method 6: Hexacarbonylmolybdenum(0)-Catalyzed Oxidation of Enediones with tert-Butyl Hydroperoxide To Form Peroxypyranones 246
38.6.1.7 Method 7: Synthesis of Functionalized Allylic Peroxides from Allylic Peroxy Vinylstannanes 247
38.6.1.7.1 Variation 1: N-Iodosuccinimide-Mediated Formation of Allylic Peroxy Vinyl Iodides 248
38.6.1.7.2 Variation 2: Palladium-Mediated C--C Bond-Forming Reactions for the Synthesis of Functionalized Allylic Peroxides 248
38.6.1.8 Method 8: Synthesis of Allylic Peroxides via the Wittig Alkenation of a-Peroxy-Substituted Aldehydes 250
38.6.1.9 Method 9: Formation of 4-(tert-Butylperoxy)cyclohexadienones by Oxidation of Phenols 251
38.6.1.9.1 Variation 1: Metal-Catalyzed Oxidation of Phenols with tert-Butyl Hydroperoxide 251
38.6.1.9.2 Variation 2: Free-Radical Oxidation of Phenols by a Hypervalent (tert-Butylperoxy)iodane and tert-Butyl Hydroperoxide 253
38.6.1.10 Method 10: Formation of Allylic 1,4-Diperoxides from the Chloroperoxidase-Catalyzed Oxidation of Conjugated Dienoic Esters 253
38.7 Product Class 7: Benzylic Peroxides 258
38.7.1 Synthesis of Product Class 7 258
38.7.1.1 Oxidation with Oxygen 258
38.7.1.1.1 Method 1: Oxidation of Arylalkanes 258
38.7.1.1.2 Method 2: Oxidation of Triarylmethyl Chlorides 259
38.7.1.1.3 Method 3: Oxidation of Arylalkenes via Trapping Reactions 259
38.7.1.1.3.1 Variation 1: Intramolecular Cyclization in the Presence of a Cobalt(II) Complex 259
38.7.1.1.3.2 Variation 2: Intermolecular Cycloaddition with Carbonyl Compounds 260
38.7.1.1.3.3 Variation 3: Intermolecular Cyclization with ß-Oxo Carbonyl Compounds in the Presence of Manganese Catalysts 261
38.7.1.1.3.4 Variation 4: Intermolecular Cyclization with Heterocyclic 1,3-Dicarbonyl Compounds in the Presence of Manganese Catalysts 263
38.7.1.2 Oxidation with Hydroperoxides 265
38.7.1.2.1 Method 1: Oxidation of Arylalkanes under Metal Catalysis 265
38.7.1.2.1.1 Variation 1: Using Chromium 265
38.7.1.2.1.2 Variation 2: Using Cobalt 266
38.7.1.2.1.3 Variation 3: Using Copper 267
38.7.1.2.1.4 Variation 4: Using Lead 270
38.7.1.2.2 Method 2: Nucleophilic Substitution Using Hydroperoxides 271
38.7.1.2.2.1 Variation 1: Of Halides 271
38.7.1.2.2.2 Variation 2: Of Alcohols 274
38.7.1.2.2.3 Variation 3: Of Imidates 276
38.7.1.2.2.4 Variation 4: Of Oxiranes 276
38.7.1.2.3 Method 3: Addition Reactions of Hydroperoxides 277
38.7.1.2.3.1 Variation 1: Acid-Mediated Addition to Alkenes 277
38.7.1.2.3.2 Variation 2: Base-Mediated Addition to Alkenes 278
38.7.1.2.3.3 Variation 3: Palladium-Mediated Addition to Alkenes 279
38.7.1.2.3.4 Variation 4: Mercury-Mediated Addition to Alkenes 280
38.7.1.2.3.5 Variation 5: Addition to Cyclopropanes 281
38.7.1.2.3.6 Variation 6: Addition to Carbonyl Compounds 283
38.7.1.3 Photooxygenation 284
38.7.1.3.1 Method 1: Photooxygenation of Arylalkenes 284
38.7.1.3.2 Method 2: Photooxygenation of Three-Membered Heterocycles via Photoinduced Electron Transfer 285
38.7.1.3.3 Method 3: Photooxygenation of Cyclopropanes via Photoinduced Radical Production 287
38.7.1.4 Other Methods 287
38.7.1.4.1 Method 1: Oxidative Fluorodesulfuration 287
38.7.1.4.2 Method 2: Ozonization of Unsaturated Benzylic Hydroperoxides 288
38.7.1.4.3 Method 3: Oxygenation of Aryl Azo Hydroperoxides 289
38.7.1.4.4 Method 4: Acid-Catalyzed Reaction of Peroxyketals with Ketene Silyl Acetals 289
38.7.2 Applications of Product Class 7 in Organic Synthesis 291
38.7.2.1 Method 1: Oxidation to Carbonyl Derivatives 291
38.7.2.2 Method 2: Reduction to Alcohols 292
38.7.2.3 Method 3: Heterolysis of an O--O or C--O Bond 292
38.7.2.3.1 Variation 1: Trapping with Alkenes 294
38.7.2.3.2 Variation 2: Trapping with Carbonyl Compounds 295
38.7.2.3.3 Variation 3: Trapping with Hydrazine Derivatives or Hydroxylamine 296
38.7.2.4 Method 4: Homolysis of the O--O Bond: Radical Production 297
38.8 Product Class 8: Monocyclic Peroxides 302
38.8.1 Product Subclass 1: Three-Membered Cyclic Peroxides (Dioxiranes) 302
38.8.1.1 Synthesis of Product Subclass 1 302
38.8.1.1.1 Method 1: Preparation of Dioxiranes Using Oxone 303
38.8.1.2 Applications of Product Subclass 1 in Organic Synthesis 305
38.8.1.2.1 Method 1: Oxidation of Heteroatoms by Dioxiranes 305
38.8.1.2.1.1 Variation 1: Synthesis of Sulfinic Acids 306
38.8.1.2.1.2 Variation 2: Synthesis of Sulfoxides and Sulfones 306
38.8.1.2.1.3 Variation 3: Synthesis of Sulfoximides 310
38.8.1.2.1.4 Variation 4: Synthesis of N-Oxides and Nitro Compounds 310
38.8.1.2.1.5 Variation 5: Synthesis of Hydroxylamines 314
38.8.1.2.1.6 Variation 6: Synthesis of Nitrones and Nitroxide Radicals 316
38.8.1.2.1.7 Variation 7: Synthesis of Hydroxamic Acids 319
38.8.1.2.1.8 Variation 8: Cleavage of C==N Bonds 320
38.8.1.2.1.9 Variation 9: Cleavage of C==P Bonds 324
38.8.1.2.1.10 Variation 10: Cleavage of C==S Bonds 325
38.8.1.2.2 Method 2: Oxidation of C==C p-Bonds by Dioxiranes 327
38.8.1.2.2.1 Variation 1: Oxidation of Alkenes 327
38.8.1.2.2.2 Variation 2: Oxidation of Allenes 327
38.8.1.2.2.3 Variation 3: Oxidation of Enolates 330
38.8.1.2.2.4 Variation 4: Oxidation of Arenes 333
38.8.1.2.2.5 Variation 5: Oxidation of Alkynes 337
38.8.1.2.3 Method 3: Oxidation of X--H s-Bonds by Dioxiranes 337
38.8.1.2.3.1 Variation 1: Oxidation of Si--H s-Bonds 337
38.8.1.2.3.2 Variation 2: Oxidation C--H s-Bonds of Saturated Alkanes 338
38.8.1.2.3.3 Variation 3: Oxidation of Activated C--H s-Bonds 341
38.8.1.2.4 Method 4: Oxidation of Organometallic Compounds by Dioxiranes 343
38.8.2 Product Subclass 2: Four-Membered Cyclic Peroxides (1,2-Dioxetanes and 1,2-Dioxetanones) 350
38.8.2.1 Synthesis of Product Subclass 2 351
38.8.2.1.1 Method 1: Cyclization of Halo Hydroperoxides 351
38.8.2.1.1.1 Variation 1: Cyclization of Epoxy Hydroperoxides 353
38.8.2.1.1.2 Variation 2: Cyclization of Unsaturated Hydroperoxides 353
38.8.2.1.1.3 Variation 3: By Cyclomercuration of Allylic Hydroperoxides 355
38.8.2.1.1.4 Variation 4: 1,2-Dioxetanones from a-Hydroperoxy Acids 355
38.8.2.1.2 Method 2: Singlet Oxygenation of Alkenes 356
38.8.2.1.2.1 Variation 1: By Sensitized Photooxygenation 357
38.8.2.1.2.2 Variation 2: Using Calcium Peroxide--Hydrogen Peroxide Complex 360
38.8.2.1.2.3 Variation 3: Using Sodium Molybdate/Hydrogen Peroxide 361
38.8.2.1.2.4 Variation 4: Using Triethylsilyl Hydrotrioxide 362
38.8.2.1.3 Method 3: Triplet Oxygenation of Cyclobutadienes 362
38.8.2.1.4 Method 4: Photocatalytic Oxygenation 363
38.8.2.1.5 Method 5: Ozonolysis of Vinylsilanes 364
38.8.2.1.6 Method 6: Oxygenation Using Phosphite Ozonides 365
38.8.2.1.6.1 Variation 1: 1,2-Dioxetanones from Photooxygenation of Ketenes 367
38.8.2.1.7 Method 7: Electron-Transfer Oxygenation 367
38.8.3 Product Subclass 3: Five-Membered Cyclic Peroxides with No Further Heteroatoms in the Ring (1,2-Dioxolanes and 1,2-Dioxolan-3-ones) 372
38.8.3.1 Synthesis of Product Subclass 3 373
38.8.3.1.1 Method 1: Cyclization of Hydroperoxides 373
38.8.3.1.1.1 Variation 1: Of Bromo Hydroperoxides 373
38.8.3.1.1.2 Variation 2: Of Epoxy Hydroperoxides 374
38.8.3.1.1.3 Variation 3: Of Vinyl Hydroperoxides 374
38.8.3.1.1.4 Variation 4: Of Stannylalkenyl Hydroperoxides 376
38.8.3.1.1.5 Variation 5: Of a-Alkoxy Hydroperoxides 377
38.8.3.1.1.6 Variation 6: Lead(IV) Acetate Mediated Cyclization of 3-Phenylpropyl Hydroperoxides 377
38.8.3.1.2 Method 2: Cyclization of Haloalkyl Peroxides 378
38.8.3.1.3 Method 3: Cyclization of Oxetane Hydroperoxyacetals 378
38.8.3.1.4 Method 4: Oxidation of a,ß-Unsaturated Ketones by Hydrogen Peroxide 380
38.8.3.1.5 Method 5: Peroxymercuration/Demercuration 382
38.8.3.1.6 Method 6: Cycloaddition of Carbonyl Oxides to C--C Multiple Bonds 383
38.8.3.1.6.1 Variation 1: From 1,2,4-Trioxolanes 383
38.8.3.1.6.2 Variation 2: Via Peroxycarbenium Ions 385
38.8.3.1.7 Method 7: Singlet Oxygenation 386
38.8.3.1.7.1 Variation 1: Of 2-Methylacrylic Acids, Leading to 3-Hydroperoxy Acids 386
38.8.3.1.7.2 Variation 2: Of Enones 387
38.8.3.1.7.3 Variation 3: Of Cyclopropanes 388
38.8.3.1.7.4 Variation 4: Of a,ß-Unsaturated Aldimines 389
38.8.3.1.8 Method 8: Radical-Mediated Oxygenation 389
38.8.3.1.8.1 Variation 1: Addition of Molecular Oxygen to Cyclopropanes 389
38.8.3.1.8.2 Variation 2: From Stable Schlenk Hydrocarbon Diradicals 393
38.8.3.1.8.3 Variation 3: Peroxidation of 1,4-Dienes and Vinylcyclopropanes with Cobalt(II)/Oxygen/Triethylsilane 394
38.8.3.1.8.4 Variation 4: Photolysis or Thermolysis of Alkylidene Azoalkanes 395
38.8.3.1.8.5 Variation 5: Thiol--Alkene Co-oxygenation 396
38.8.3.1.8.6 Variation 6: Halogen-Mediated Peroxidations 397
38.8.3.1.9 Method 9: ß-Fragmentation of Alkoxy Radicals 397
38.8.3.1.10 Method 10: Synthesis from Benzo-Fused Bicyclic Sulfonium Salts 399
38.8.3.1.11 Method 11: Ozonolysis 400
38.8.3.1.12 Method 12: Peroxide Addition 402
38.8.4 Product Subclass 4: Five-Membered Cyclic Peroxides with One Further Oxygen Atom in the Ring (1,2,4-Trioxolanes) 406
38.8.4.1 Synthesis of Product Subclass 4 407
38.8.4.1.1 Method 1: Ozonolysis of Alkenes 407
38.8.4.1.2 Method 2: Cycloaddition of Carbonyl Oxides to C==O Bonds 412
38.8.4.1.2.1 Variation 1: From the Ozonolysis of Cycloalkadienes in the Presence of Carbonyl Compounds 414
38.8.4.1.2.2 Variation 2: Griesbaum Co-ozonolysis 414
38.8.4.1.3 Method 3: Ozonolysis of Acetylenic Substrates 416
38.8.4.1.4 Method 4: Photooxygenation 417
38.8.4.1.4.1 Variation 1: Of Epoxides 417
38.8.4.1.4.2 Variation 2: Of Furans 418
38.8.4.1.4.3 Variation 3: Of Diazo Compounds and Azines 419
38.8.5 Product Subclass 5: Six-Membered Cyclic Peroxides with No Further Heteroatoms in the Ring (1,2-Dioxanes and 3,6-Dihydro-1,2-dioxins) 424
38.8.5.1 Synthesis of Product Subclass 5 425
38.8.5.1.1 Method 1: Cyclization of Hydroperoxides 425
38.8.5.1.1.1 Variation 1: Cyclization of Halo Hydroperoxides 425
38.8.5.1.1.2 Variation 2: Cyclization of Epoxy Hydroperoxides 426
38.8.5.1.1.3 Variation 3: Cyclization of Vinyl Hydroperoxides 427
38.8.5.1.1.4 Variation 4: Cyclization of Oxetane Hydroperoxides 428
38.8.5.1.2 Method 2: Cyclization of Unsaturated Hydroperoxyacetals 429
38.8.5.1.3 Method 3: Cycloaddition of Carbonyl Oxides to C--C Multiple Bonds 431
38.8.5.1.4 Method 4: Ozonolysis of Alkylidenecyclopropanes 433
38.8.5.1.5 Method 5: Singlet Oxygenation of 1,3-Dienes and Related Compounds 434
38.8.5.1.6 Method 6: Radical-Mediated Oxygenation 436
38.8.5.1.6.1 Variation 1: Thiol--Alkene Co-oxygenation 436
38.8.5.1.6.2 Variation 2: Free-Radical Cyclization of Alkenes with Carbonyl Compounds 436
38.8.5.1.6.3 Variation 3: Peroxyl-Radical Cyclization 438
38.8.5.1.6.4 Variation 4: Peroxidation with Cobalt(II)/Oxygen/Triethylsilane 439
38.8.5.1.6.5 Variation 5: Oxygen Addition to Carbon-Centered Radicals 440
38.8.5.1.6.6 Variation 6: Lead(IV) Acetate Mediated Cyclization of .-Phenyl Hydroperoxides 441
38.8.5.1.6.7 Variation 7: Addition of Molecular Oxygen to Alkenes 441
38.8.5.1.7 Method 7: Photoenolization and Oxygenation of a,ß-Unsaturated Ketones 442
38.8.5.1.8 Method 8: Nucleophilic Addition of Peroxides 444
38.8.6 Product Subclass 6: Six-Membered Cyclic Peroxides with One Further Oxygen Atom in the Ring (1,2,4-Trioxanes) 448
38.8.6.1 Synthesis of Product Subclass 6 449
38.8.6.1.1 Method 1: Synthesis from Hydroperoxides 449
38.8.6.1.1.1 Variation 1: Condensation of ß-Hydroperoxy Alcohols with Aldehydes or Ketones 449
38.8.6.1.1.2 Variation 2: Cyclization of Unsaturated Hydroperoxyacetals 454
38.8.6.1.1.3 Variation 3: Autoxidation of Unsaturated Hydroperoxyacetals 457
38.8.6.1.1.4 Variation 4: From Epoxy Hydroperoxides 458
38.8.6.1.2 Method 2: Cyclization of Allylic Peroxyhemiketals 458
38.8.6.1.2.1 Variation 1: Mercury(II)-Mediated Cyclization of Unsaturated Peroxyhemiketals 459
38.8.6.1.3 Method 3: Cyclization of Silyl Peroxyhemiketals in the Presence of Aldehydes and Ketones 460
38.8.6.1.3.1 Variation 1: 1,2,4-Trioxan-5-ones from a-(Trimethylsilylperoxy) Esters 460
38.8.6.1.4 Method 4: Photooxygenation 461
38.8.6.1.5 Method 5: Synthesis from 1,2-Dioxetanes: The Posner Reaction 462
38.8.6.1.6 Method 6: Miscellaneous Methods Employing Bridged Cyclic Peroxides 466
38.8.6.1.7 Method 7: Addition of Oxygen to Allylic Hydroperoxides 468
38.8.6.1.8 Method 8: Trapping of Paterno--Büchi 1,4-Diradicals by Molecular Oxygen 471
38.8.6.1.9 Method 9: Autoxidation of Imines in the Presence of Aldehydes 472
38.8.7 Product Subclass 7: Six-Membered Cyclic Peroxides with Two Further Oxygen Atoms in the Ring (1,2,4,5-Tetroxanes) 476
38.8.7.1 Synthesis of Product Subclass 7 477
38.8.7.1.1 Method 1: Synthesis from Aldehydes or Ketones 477
38.8.7.1.1.1 Variation 1: Reaction of Aldehydes or Ketones with Bis(trimethylsilyl) Peroxide 483
38.8.7.1.2 Method 2: Synthesis by Ozonolysis 485
38.8.7.1.2.1 Variation 1: Of O-Methyloximes 488
38.8.7.1.3 Method 3: Synthesis from 1,2,4-Trioxolanes 489
38.8.7.1.4 Methods 4: Miscellaneous Methods 490
38.9 Product Class 9: Larger-Ring Cyclic Peroxides and Endoperoxides 496
38.9.1 Synthesis of Product Class 9 496
38.9.1.1 Method 1: Peroxidation with Triplet Molecular Oxygen 496
38.9.1.1.1 Variation 1: Cycloaddition of Triplet Dioxygen to Biradicals 496
38.9.1.1.2 Variation 2: Cycloaddition of Triplet Oxygen to an o-Quinodimethane System 497
38.9.1.1.3 Variation 3: Electron-Transfer-Induced Photooxidation of 1,6-Dienes with Triplet Oxygen 498
38.9.1.1.4 Variation 4: Lewis Acid Induced Peroxidation of 1,3-Dienes 500
38.9.1.1.5 Variation 5: Autoxidation of Nonconjugated 1,4-Dienes 501
38.9.1.1.6 Variation 6: Thiol--Alkene Co-oxygenation 502
38.9.1.1.7 Variation 7: Cobalt(II)-Catalyzed Peroxidation of 1,5-Dienes with Molecular Oxygen and Triethylsilane 505
38.9.1.2 Method 2: Oxidation of Cyclic Unsaturated Compounds with Photochemically Generated Singlet Oxygen 506
38.9.1.2.1 Variation 1: Photooxidation of Naphthalene Derivatives 507
38.9.1.2.2 Variation 2: Photooxidation of Anthracene and Pentacene Derivatives 510
38.9.1.2.3 Variation 3: Photooxidation of Strained Metacyclophanes 512
38.9.1.2.4 Variation 4: Photooxidation of Cyclopentadiene and Cyclohexa-1,3- or Cyclohexa-1,4-diene Systems 512
38.9.1.2.5 Variation 5: Photooxidation of Cycloheptadiene/triene Systems 515
38.9.1.2.6 Variation 6: Photooxidation of Cyclooctadiene/triene/tetraene Systems 519
38.9.1.3 Method 3: Oxidation of Cyclic Unsaturated Compounds by Chemically Generated Singlet Oxygen 520
38.9.1.4 Method 4: Cyclization of Hydroperoxides and Their Derivatives through Nucleophilic Substitution 521
38.9.1.4.1 Variation 1: Cyclization of Bromo Hydroperoxides 521
38.9.1.4.2 Variation 2: Acid-Catalyzed Cyclization of Epoxy Hydroperoxides 523
38.9.1.4.3 Variation 3: Trimethylsilyl Trifluoromethanesulfonate Catalyzed Intramolecular Cyclization of Silyl Peroxides 523
38.9.1.4.4 Variation 4: Peroxide Transfer from Bis(tributyltin) Peroxide 524
38.9.1.4.5 Variation 5: Cesium Hydroxide or Silver(I) Oxide Mediated Cycloalkylation of Alkane-1,1-diyl Dihydroperoxides and Dihaloalkanes 525
38.9.1.4.6 Variation 6: Base-Catalyzed Cyclization of Dihydroperoxides and Dialkyldichlorosilanes 526
38.9.1.5 Method 5: Cyclization of Unsaturated Hydroperoxides through Intramolecular Nucleophilic Addition 527
38.9.1.5.1 Variation 1: Halonium Ion Mediated Cyclization of Unsaturated Hydroperoxides 527
38.9.1.5.2 Variation 2: Base-Catalyzed Intramolecular Cyclization of Unsaturated Hydroperoxides 531
38.9.1.5.3 Variation 3: Ozonolysis of Unsaturated Hydroperoxides 532
38.9.1.5.4 Variation 4: Ozonolysis of Vinylsilanes 535
38.9.1.5.5 Variation 5: Peroxymercuration/Demercuration of Cyclic Dienes 536
38.9.1.5.6 Variation 6: Intramolecular Capture of ß-Hydroperoxy Cations 537
38.9.1.6 Method 6: Cycloaddition of Peroxides with Carbonyl Compounds 538
38.9.1.6.1 Variation 1: Trimethylsilylation of Dihydroperoxides Followed by Trimethylsilyl Trifluoromethanesulfonate Catalyzed Cyclocondensation with Carbonyl Compounds 538
38.9.1.6.2 Variation 2: Acid-Catalyzed Condensation of .- or d-Hydroxy Hydroperoxides and Ketones 539
38.9.1.6.3 Variation 3: Acid-Catalyzed Condensation of 3-Methyl-3-(triethylsilylperoxy)butan-1-ol and Carbonyl Compounds 541
38.9.1.7 Method 7: Synthesis with Retention of the Functional Group 542
38.9.1.7.1 Variation 1: Reduction of C==C Bonds in Unsaturated Bicyclic Peroxides 542
38.9.1.7.2 Variation 2: Chlorination of Unsaturated Bicyclic Peroxides 544
38.9.1.7.3 Variation 3: Selective Reduction of the Hydroperoxide Group in Hydroperoxy Endoperoxides 544
38.9.1.7.4 Variation 4: Dehydration of Hydroperoxy-Substituted Endoperoxides 544
38.9.1.7.5 Variation 5: Reduction of a Ketone Group in Endoperoxides 546
38.9.1.7.6 Variation 6: Oxidation of Hydroxy Endoperoxides 546
38.9.1.7.7 Variation 7: Diels--Alder Reaction with Dimethyl 1,2,4,5-Tetrazine-3,6-dicarboxylate 547
38.9.1.7.8 Variation 8: Reductive Debromination with Tributyltin Hydride 547
38.9.1.7.9 Variation 9: Silver(I) Oxide Mediated Methylation of Hydroperoxy-Substituted Endoperoxides 548
Keyword Index 552
Author Index 582
Abbreviations 604