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Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 26

Ketones
Georg Thieme Verlag KGerschienen am01.07.2014
Turning Information into Knowledge

Science of Synthesis: Houben-Weyl Methods of Molecular Transformations is the entirely new edition of the acclaimed reference series Houben-Weyl, the standard synthetic chemistry resource since 1909. This new edition is published in English and will comprise 48 volumes published between the years 2000 and 2008.

Science of Synthesis is a quality reference work developed by a highly esteemed editorial board to provide a comprehensive and critical selection of reliable organic and organometallic synthetic methods. This unique resource is designed to be the first point of reference when searching for a synthesis strategy.
Contains the expertise of presently 400 leading chemists worldwide. Critically evaluates the preparative applicability and significance of the synthetic methods. Discusses relevant background information and provides detailed experimental procedures

For full information on the Science of Synthesis series, visit the Science of Synthesis Homepage Series Editors: D. Bellus, S. V. Ley, R. Noyori, M. Regitz, E. Schaumann, I. Shinkai, E. J. Thomas, B. M. Trost, P. J. Reider.


Cossymehr
Verfügbare Formate
BuchGebunden (Leinen)
EUR1.999,99
EUR1.999,99

Produkt

KlappentextTurning Information into Knowledge

Science of Synthesis: Houben-Weyl Methods of Molecular Transformations is the entirely new edition of the acclaimed reference series Houben-Weyl, the standard synthetic chemistry resource since 1909. This new edition is published in English and will comprise 48 volumes published between the years 2000 and 2008.

Science of Synthesis is a quality reference work developed by a highly esteemed editorial board to provide a comprehensive and critical selection of reliable organic and organometallic synthetic methods. This unique resource is designed to be the first point of reference when searching for a synthesis strategy.
Contains the expertise of presently 400 leading chemists worldwide. Critically evaluates the preparative applicability and significance of the synthetic methods. Discusses relevant background information and provides detailed experimental procedures

For full information on the Science of Synthesis series, visit the Science of Synthesis Homepage Series Editors: D. Bellus, S. V. Ley, R. Noyori, M. Regitz, E. Schaumann, I. Shinkai, E. J. Thomas, B. M. Trost, P. J. Reider.


Cossy
Details
Weitere ISBN/GTIN9783131720115
ProduktartE-Book
EinbandartE-Book
FormatPDF
Erscheinungsjahr2014
Erscheinungsdatum01.07.2014
Seiten1422 Seiten
SpracheEnglisch
Dateigrösse16691
Artikel-Nr.1551495
Rubriken
Genre9200

Inhalt/Kritik

Inhaltsverzeichnis
1;Science of Synthesis - Volume 26: Ketones;1
1.1;Title page;3
1.2;Imprint;5
1.3;Preface;6
1.4;Volume Editor's Preface;8
1.5;Overview;10
1.6;Table of Contents;12
1.7;Introduction;46
1.8;26.1 Product Class 1: Aliphatic and Alicyclic Ketones (Excluding Cyclobutanones and Cyclopropanones);58
1.8.1;26.1.1 Synthesis by Oxidation of Heterosubstituted Alkanes;84
1.8.1.1;26.1.1.1 Oxidation of Halides;85
1.8.1.1.1;26.1.1.1.1 Method 1: With Sodium Dichromate or Sodium Periodate;85
1.8.1.1.2;26.1.1.1.2 Method 2: With Dimethyl Sulfoxide;85
1.8.1.1.3;26.1.1.1.3 Method 3: With Nitrogen--Oxygen Compounds;86
1.8.1.2;26.1.1.2 Oxidation of Secondary Alcohols;87
1.8.1.2.1;26.1.1.2.1 Method 1: By Hydrogen Elimination;87
1.8.1.2.2;26.1.1.2.2 Method 2: With Chromium(VI) Compounds;88
1.8.1.2.2.1;26.1.1.2.2.1 Variation 1: With Chromic Acid in Aqueous Solution;89
1.8.1.2.2.2;26.1.1.2.2.2 Variation 2: With Chromic Acid in Acetic Acid;89
1.8.1.2.2.3;26.1.1.2.2.3 Variation 3: With Chromic Acid in Acetone;91
1.8.1.2.2.4;26.1.1.2.2.4 Variation 4: With Chromic Acid in a Two-Phase System;92
1.8.1.2.2.5;26.1.1.2.2.5 Variation 5: With Chromium(VI) Oxide in Pyridine;94
1.8.1.2.2.6;26.1.1.2.2.6 Variation 6: With Halochromates;96
1.8.1.2.3;26.1.1.2.3 Method 3: With Manganese Compounds;98
1.8.1.2.3.1;26.1.1.2.3.1 Variation 1: With Permanganate;98
1.8.1.2.3.2;26.1.1.2.3.2 Variation 2: With Manganese(IV) Oxide;100
1.8.1.2.4;26.1.1.2.4 Method 4: With Other Metal Compounds;103
1.8.1.2.4.1;26.1.1.2.4.1 Variation 1: With Iron Compounds;103
1.8.1.2.4.2;26.1.1.2.4.2 Variation 2: With Ruthenium(VIII) Oxide;104
1.8.1.2.4.3;26.1.1.2.4.3 Variation 3: With Copper(II) Salts;105
1.8.1.2.5;26.1.1.2.5 Method 5: Oxidation of Secondary Alcohols with Halogen Compounds;105
1.8.1.2.5.1;26.1.1.2.5.1 Variation 1: With Hypofluorous Acid;105
1.8.1.2.5.2;26.1.1.2.5.2 Variation 2: With Hypochlorite and Related Oxidants;106
1.8.1.2.5.3;26.1.1.2.5.3 Variation 3: With N-tert-Butylbenzenesulfinimidoyl Chloride;109
1.8.1.2.5.4;26.1.1.2.5.4 Variation 4: With Bromo Compounds;110
1.8.1.2.5.5;26.1.1.2.5.5 Variation 5: With Periodate;112
1.8.1.2.5.6;26.1.1.2.5.6 Variation 6: With Organic Iodine(V) Compounds;113
1.8.1.2.5.7;26.1.1.2.5.7 Variation 7: With Organic Iodine(III) Compounds;116
1.8.1.2.6;26.1.1.2.6 Method 6: Oxidation by Molecular Oxygen;119
1.8.1.2.6.1;26.1.1.2.6.1 Variation 1: With Ruthenium-Based Catalysts;119
1.8.1.2.6.2;26.1.1.2.6.2 Variation 2: With Cobalt-Based Catalysts;120
1.8.1.2.6.3;26.1.1.2.6.3 Variation 3: With Vanadium-Based Catalysts;121
1.8.1.2.6.4;26.1.1.2.6.4 Variation 4: With Copper-Based Catalysts;123
1.8.1.2.6.5;26.1.1.2.6.5 Variation 5: With Palladium-Based Catalysts;124
1.8.1.2.6.6;26.1.1.2.6.6 Variation 6: With Other Reagents;127
1.8.1.2.7;26.1.1.2.7 Method 7: Oxidation with Hydrogen Peroxide;128
1.8.1.2.8;26.1.1.2.8 Method 8: Oxidation with Hydroperoxides and Peracids;129
1.8.1.2.8.1;26.1.1.2.8.1 Variation 1: With tert-Butyl Hydroperoxide;130
1.8.1.2.8.2;26.1.1.2.8.2 Variation 2: With Peracids;131
1.8.1.2.9;26.1.1.2.9 Method 9: Oxidation with Dioxiranes;133
1.8.1.2.10;26.1.1.2.10 Method 10: Oxidation with Dimethyl Sulfoxide;134
1.8.1.2.11;26.1.1.2.11 Method 11: Oxidation with Peroxomonosulfate;140
1.8.1.2.12;26.1.1.2.12 Method 12: Oxidation with Nitrogen Compounds;141
1.8.1.2.12.1;26.1.1.2.12.1 Variation 1: With Organic Oxoammonium Salts;141
1.8.1.2.12.2;26.1.1.2.12.2 Variation 2: With N-Oxides;143
1.8.1.2.12.3;26.1.1.2.12.3 Variation 3: With Other Nitrogen-Based Oxidants;143
1.8.1.2.13;26.1.1.2.13 Method 13: Oppenauer Oxidation;144
1.8.1.2.14;26.1.1.2.14 Method 14: Dehydrogenation with Alkenes and Alkynes;147
1.8.1.2.14.1;26.1.1.2.14.1 Variation 1: With Alkenes;148
1.8.1.2.14.2;26.1.1.2.14.2 Variation 2: By Isomerization of Allyl Alcohols;148
1.8.1.2.14.3;26.1.1.2.14.3 Variation 3: By Isomerization of a-Hydroxyalkynes
;149
1.8.1.2.15;26.1.1.2.15 Method 15: Other Methods;150
1.8.1.3;26.1.1.3 Oxidation of Secondary Alcohol Derivatives;153
1.8.1.3.1;26.1.1.3.1 Method 1: Oxidation of Ethers;153
1.8.1.3.2;26.1.1.3.2 Method 2: Oxidative Deprotection of Silyl Ethers;156
1.8.1.4;26.1.1.4 Oxidation of Nitrogen Compounds;158
1.8.1.4.1;26.1.1.4.1 Method 1: From Nitroalkanes (The Nef Reaction);158
1.8.1.4.2;26.1.1.4.2 Method 2: From Amines;160
1.8.2;26.1.2 Synthesis by Oxidation of Alkenes and Alkanes (Excluding Allylic or Benzylic Derivatives);172
1.8.2.1;26.1.2.1 Method 1: Oxidation of Alkenes without Cleavage of the Skeleton;172
1.8.2.1.1;26.1.2.1.1 Variation 1: Using Mercury Salts;172
1.8.2.1.2;26.1.2.1.2 Variation 2: Using Palladium Salts with Oxygen and a Copper Cocatalyst or Other Oxidant Systems;173
1.8.2.1.3;26.1.2.1.3 Variation 3: Using Rhodium Salts with Oxygen;176
1.8.2.1.4;26.1.2.1.4 Variation 4: By Oxidation of Intermediate Boron Adducts;176
1.8.2.2;26.1.2.2 Method 2: Oxidation of Alkenes with Cleavage of a C==C Bond;178
1.8.2.2.1;26.1.2.2.1 Variation 1: Using Transition Metal Compounds;179
1.8.2.2.2;26.1.2.2.2 Variation 2: Using Permanganate and Periodate Reagents;179
1.8.2.2.3;26.1.2.2.3 Variation 3: By Ozonolysis;180
1.8.2.2.4;26.1.2.2.4 Variation 4: By Other Methods;181
1.8.2.3;26.1.2.3 Method 3: Transition-Metal-Catalyzed Oxidation of Alkanes;182
1.8.2.3.1;26.1.2.3.1 Variation 1: Using Oxygen;182
1.8.2.3.2;26.1.2.3.2 Variation 2: Using Ozone;185
1.8.2.3.3;26.1.2.3.3 Variation 3: Using Hydrogen Peroxide and Organic Peroxides;185
1.8.2.3.4;26.1.2.3.4 Variation 4: Using Sodium Periodate;189
1.8.2.3.5;26.1.2.3.5 Variation 5: Using Iodosylbenzene;190
1.8.2.3.6;26.1.2.3.6 Variation 6: Under Irradiation;191
1.8.2.4;26.1.2.4 Method 4: Oxidation of Alkanes by Other Methods;191
1.8.2.4.1;26.1.2.4.1 Variation 1: Using Chromates and Permanganates under Lewis Acid Catalysis;191
1.8.2.4.2;26.1.2.4.2 Variation 2: Using Dioxiranes;192
1.8.2.4.3;26.1.2.4.3 Variation 3: Using Ozone;193
1.8.2.4.4;26.1.2.4.4 Variation 4: Electrochemical Oxidation;193
1.8.3;26.1.3 Synthesis by Reduction of 1,2-Diketones and a-Diazo Ketones, a,a-Dihetero- and a-Heterosubstituted Ketones, Enones, and Ynones
;198
1.8.4;26.1.3 Synthesis by Reduction of 1,2-Diketones and a-Diazo Ketones, a,a-Dihetero- and a-Heterosubstituted Ketones, Enones, and Ynones ;198
1.8.4.1;26.1.3.1 Reduction of 1,2-Diketones and a-Diazo Ketones
;198
1.8.4.1.1;26.1.3.1.1 Method 1: Reduction of 1,2-Diketones;198
1.8.4.1.2;26.1.3.1.2 Method 2: Reduction of a-Diazo Ketones
;200
1.8.4.2;26.1.3.2 Reduction of a,a-Diheterosubstituted Ketones
;202
1.8.4.2.1;26.1.3.2.1 Method 1: Reduction of a,a-Dihalo Ketones
;202
1.8.4.2.2;26.1.3.2.2 Method 2: Reduction of a-Oxo Thioacetals
;203
1.8.4.3;26.1.3.3 Reduction of a-Heterosubstituted Ketones
;205
1.8.4.3.1;26.1.3.3.1 Reduction of a-Silylated Ketones
;205
1.8.4.3.1.1;26.1.3.3.1.1 Method 1: Acidic Conditions;206
1.8.4.3.1.2;26.1.3.3.1.2 Method 2: Basic Conditions;207
1.8.4.3.2;26.1.3.3.2 Reduction of a-Halo Ketones
;208
1.8.4.3.2.1;26.1.3.3.2.1 Method 1: Reduction of a-Fluoro Ketones
;210
1.8.4.3.2.2;26.1.3.3.2.2 Method 2: Reduction of a-Chloro Ketones
;211
1.8.4.3.2.2.1;26.1.3.3.2.2.1 Variation 1: Active Metals and Salts;211
1.8.4.3.2.2.2;26.1.3.3.2.2.2 Variation 2: Nucleophilic Reagents;212
1.8.4.3.2.2.3;26.1.3.3.2.2.3 Variation 3: Hydrides;214
1.8.4.3.2.3;26.1.3.3.2.3 Method 3: Reduction of a-Bromo Ketones
;215
1.8.4.3.2.3.1;26.1.3.3.2.3.1 Variation 1: Active Metals or Salts and Electrolysis;215
1.8.4.3.2.3.2;26.1.3.3.2.3.2 Variation 2: Nucleophilic Reagents;217
1.8.4.3.2.3.3;26.1.3.3.2.3.3 Variation 3: Hydrides;218
1.8.4.3.2.4;26.1.3.3.2.4 Method 4: Reduction of a-Iodo Ketones;220
1.8.4.3.3;26.1.3.3.3 Reduction of a-Oxygenated Ketones;221
1.8.4.3.3.1;26.1.3.3.3.1 Method 1: Reduction of a-Hydroxy Ketones;222
1.8.4.3.3.1.1;26.1.3.3.3.1.1 Variation 1: Active Metals and Salts;222
1.8.4.3.3.1.2;26.1.3.3.3.1.2 Variation 2: Nucleophilic Reagents;223
1.8.4.3.3.2;26.1.3.3.3.2 Method 2: Reduction of a-Alkoxy, a-Acyloxy, and a-Sulfonyloxy Ketones
;225
1.8.4.3.3.2.1;26.1.3.3.3.2.1 Variation 1: Active Metals and Salts;225
1.8.4.3.3.2.2;26.1.3.3.3.2.2 Variation 2: Nucleophilic Reagents and Hydrides;227
1.8.4.3.3.3;26.1.3.3.3.3 Method 3: Reduction of a,ß-Epoxy Ketones
;229
1.8.4.3.3.3.1;26.1.3.3.3.3.1 Variation 1: Active Metals and Salts;229
1.8.4.3.3.3.2;26.1.3.3.3.3.2 Variation 2: Nucleophilic Reagents;231
1.8.4.3.4;26.1.3.3.4 Reduction of a-Sulfurated Ketones
;232
1.8.4.3.4.1;26.1.3.3.4.1 Method 1: Reduction of a-Sulfanyl Ketones
;233
1.8.4.3.4.2;26.1.3.3.4.2 Method 2: Reduction of a-Sulfinyl Ketones
;235
1.8.4.3.4.3;26.1.3.3.4.3 Method 3: Reduction of a-Sulfonyl Ketones
;236
1.8.4.3.4.3.1;26.1.3.3.4.3.1 Variation 1: Active Metals and Salts;236
1.8.4.3.4.3.2;26.1.3.3.4.3.2 Variation 2: Radicals and Nucleophilic Reagents;240
1.8.4.3.5;26.1.3.3.5 Reduction of a-Selanyl Ketones
;240
1.8.4.3.6;26.1.3.3.6 Reduction of a-Nitrogenated Ketones
;243
1.8.4.4;26.1.3.4 Reduction of Enones;244
1.8.4.4.1;26.1.3.4.1 Method 1: Catalytic Hydrogenation;244
1.8.4.4.1.1;26.1.3.4.1.1 Variation 1: Hydrogenation under Heterogeneous Conditions;244
1.8.4.4.1.2;26.1.3.4.1.2 Variation 2: Hydrogenation under Homogeneous Conditions;247
1.8.4.4.1.3;26.1.3.4.1.3 Variation 3: Transfer Hydrogenation;249
1.8.4.4.2;26.1.3.4.2 Method 2: Reduction with Hydrides;251
1.8.4.4.2.1;26.1.3.4.2.1 Variation 1: Boron Hydrides;251
1.8.4.4.2.2;26.1.3.4.2.2 Variation 2: Aluminum Hydrides;253
1.8.4.4.2.3;26.1.3.4.2.3 Variation 3: Silicon Hydrides;255
1.8.4.4.2.4;26.1.3.4.2.4 Variation 4: Tin Hydrides and Metal Hydroselenides/Hydrotellurides;257
1.8.4.4.2.5;26.1.3.4.2.5 Variation 5: Transition Metal Hydrides;259
1.8.4.4.3;26.1.3.4.3 Method 3: Reduction with Dissolving Metals;261
1.8.4.4.3.1;26.1.3.4.3.1 Variation 1: Main Group Metals;261
1.8.4.4.3.2;26.1.3.4.3.2 Variation 2: Transition Metals and Salts;265
1.8.4.4.4;26.1.3.4.4 Methods 4: Other Methodologies;266
1.8.4.5;26.1.3.5 Reduction of Ynones;269
1.8.4.5.1;26.1.3.5.1 Method 1: Partial and Full Reduction Methodologies;269
1.8.5;26.1.4 Synthesis from Carboxylic Acids and Derivatives by Substitution with a Carbon Nucleophile;288
1.8.5.1;26.1.4.1 Method 1: Synthesis from Acyl Halides;288
1.8.5.1.1;26.1.4.1.1 Variation 1: With Organotin Reagents;289
1.8.5.1.2;26.1.4.1.2 Variation 2: With Organoboron Reagents;289
1.8.5.1.3;26.1.4.1.3 Variation 3: With Organoaluminum Reagents;290
1.8.5.1.4;26.1.4.1.4 Variation 4: With Organozinc Reagents;292
1.8.5.1.5;26.1.4.1.5 Variation 5: With Organocadmium Reagents;293
1.8.5.1.6;26.1.4.1.6 Variation 6: With Organomercury Reagents;293
1.8.5.1.7;26.1.4.1.7 Variation 7: With Organocopper Reagents;294
1.8.5.1.8;26.1.4.1.8 Variation 8: With Organocobalt, Organorhodium, or Organoiron Reagents;297
1.8.5.1.9;26.1.4.1.9 Variation 9: With Organomanganese Reagents;298
1.8.5.1.10;26.1.4.1.10 Variation 10: With Organotitanium or Organozirconium Reagents;299
1.8.5.1.11;26.1.4.1.11 Variation 11: With Grignard Reagents;300
1.8.5.1.12;26.1.4.1.12 Variation 12: With Organolithium Reagents;302
1.8.5.1.13;26.1.4.1.13 Variation 13: With Miscellaneous Organometallic Reagents;303
1.8.5.2;26.1.4.2 Method 2: Synthesis from Carboxylic Acids;303
1.8.5.2.1;26.1.4.2.1 Variation 1: With Grignard Reagents;304
1.8.5.2.2;26.1.4.2.2 Variation 2: With Organolithium Reagents;305
1.8.5.3;26.1.4.3 Method 3: Synthesis from Carboxylic Esters;306
1.8.5.3.1;26.1.4.3.1 Variation 1: With Grignard Reagents;306
1.8.5.3.2;26.1.4.3.2 Variation 2: With Organolithium or Organosodium Reagents;308
1.8.5.4;26.1.4.4 Method 4: Synthesis from Carboxylic Anhydrides;309
1.8.5.4.1;26.1.4.4.1 Variation 1: With Organosilicon Reagents;309
1.8.5.4.2;26.1.4.4.2 Variation 2: With Organotin Reagents;310
1.8.5.4.3;26.1.4.4.3 Variation 3: With Organoboron Reagents;311
1.8.5.4.4;26.1.4.4.4 Variation 4: With Organoaluminum Reagents;311
1.8.5.4.5;26.1.4.4.5 Variation 5: With Organozinc Reagents;312
1.8.5.4.6;26.1.4.4.6 Variation 6: With Organocadmium Reagents;313
1.8.5.4.7;26.1.4.4.7 Variation 7: With Organocopper Reagents;313
1.8.5.4.8;26.1.4.4.8 Variation 8: With Organomanganese Reagents;314
1.8.5.4.9;26.1.4.4.9 Variation 9: With Grignard Reagents;315
1.8.5.4.10;26.1.4.4.10 Variation 10: With Organolithium or Organosodium Reagents;316
1.8.5.5;26.1.4.5 Method 5: Synthesis from S-Alkyl or S-Aryl Thioesters;317
1.8.5.5.1;26.1.4.5.1 Variation 1: With Organosilicon or Organoboron Reagents;317
1.8.5.5.2;26.1.4.5.2 Variation 2: With Organozinc Reagents;318
1.8.5.5.3;26.1.4.5.3 Variation 3: With Organocopper Reagents;319
1.8.5.5.4;26.1.4.5.4 Variation 4: With Grignard Reagents;319
1.8.5.6;26.1.4.6 Method 6: Synthesis from Amides;320
1.8.5.6.1;26.1.4.6.1 Variation 1: With Grignard Reagents;320
1.8.5.6.2;26.1.4.6.2 Variation 2: With Organolithium Reagents;321
1.8.5.7;26.1.4.7 Method 7: Synthesis from Nitriles;322
1.8.5.7.1;26.1.4.7.1 Variation 1: With Organozinc Reagents;322
1.8.5.7.2;26.1.4.7.2 Variation 2: With Organotitanium and Organozirconium Reagents;323
1.8.5.7.3;26.1.4.7.3 Variation 3: With Grignard Reagents;323
1.8.5.7.4;26.1.4.7.4 Variation 4: With Organolithium Reagents;324
1.8.5.7.5;26.1.4.7.5 Variation 5: With Alkylidenephosphorane Reagents;324
1.8.5.8;26.1.4.8 Method 8: Synthesis from Dihydroimidazoles;325
1.8.5.8.1;26.1.4.8.1 Variation 1: With Grignard Reagents;325
1.8.5.8.2;26.1.4.8.2 Variation 2: With Organanolithium Reagents;326
1.8.5.9;26.1.4.9 Method 9: Synthesis from Miscellaneous Acylating Reagents;326
1.8.5.9.1;26.1.4.9.1 Variation 1: From Carbon Dioxide and Its Derivatives;326
1.8.5.9.2;26.1.4.9.2 Variation 2: From 5,6-Dihydro-1,3-oxazines;327
1.8.5.9.3;26.1.4.9.3 Variation 3: From 1,3-Benzoxathiol-1-ium Salts and Related Compounds;328
1.8.5.9.4;26.1.4.9.4 Variation 4: From Ortho Esters;328
1.8.5.9.5;26.1.4.9.5 Variation 5: From Acyl Cyanides;329
1.8.5.9.6;26.1.4.9.6 Variation 6: From Acylsilanes;329
1.8.6;26.1.5 Synthesis from Aldehydes by Substitution of the Aldehyde Hydrogen;338
1.8.6.1;26.1.5.1 Method 1: Radical Reaction of Aldehydes with Alkenes;338
1.8.6.2;26.1.5.2 Method 2: Addition of Diazoalkanes to Aldehydes;339
1.8.6.3;26.1.5.3 Method 3: Hydroacylation of Aldehydes;340
1.8.6.3.1;26.1.5.3.1 Variation 1: With Ruthenium Complexes;341
1.8.6.3.2;26.1.5.3.2 Variation 2: With Cobalt Complexes;341
1.8.6.3.3;26.1.5.3.3 Variation 3: With Rhodium Complexes;342
1.8.7;26.1.6 Synthesis from Thioketones, Acetals, Cyanohydrins, Enol Ethers, Enamines, Other Ene Derivatives, and Related Compounds;346
1.8.7.1;26.1.6.1 Synthesis from Thioketones;346
1.8.7.1.1;26.1.6.1.1 Method 1: Hydrolysis of Thioketones;346
1.8.7.1.2;26.1.6.1.2 Method 2: Oxidative Cleavage of Thioketones;347
1.8.7.1.3;26.1.6.1.3 Method 3: Nitrosative Cleavage of Thioketones;349
1.8.7.2;26.1.6.2 Synthesis from Iminium Ions, Ketimines, and Derivatives;349
1.8.7.2.1;26.1.6.2.1 Method 1: Hydrolysis of Iminium Salts and Imines;349
1.8.7.3;26.1.6.3 Synthesis from N-Sulfanyl- and N-Sulfonylimines;352
1.8.7.3.1;26.1.6.3.1 Method 1: Hydrolysis of N-Sulfanyl- and N-Sulfonylimines;352
1.8.7.4;26.1.6.4 Synthesis from Oximes and Derivatives;352
1.8.7.4.1;26.1.6.4.1 Method 1: Hydrolysis of Oximes and Derivatives;352
1.8.7.4.1.1;26.1.6.4.1.1 Variation 1: Sodium Hydrogen Sulfite Assisted Hydrolysis of Oximes and Derivatives;353
1.8.7.4.1.2;26.1.6.4.1.2 Variation 2: Metal Salt Assisted Hydrolysis of Oximes and Derivatives;354
1.8.7.4.2;26.1.6.4.2 Method 2: Cleavage of Oximes and Derivatives by the Exchange Method;355
1.8.7.4.3;26.1.6.4.3 Method 3: Oxidative Cleavage of Oximes and Derivatives;356
1.8.7.4.3.1;26.1.6.4.3.1 Variation 1: Aerobic Oxidation and Ozonolysis of Oximes and Derivatives;356
1.8.7.4.3.2;26.1.6.4.3.2 Variation 2: Oxidative Cleavage of Oximes and Derivatives with Peroxidic Compounds;357
1.8.7.4.3.3;26.1.6.4.3.3 Variation 3: Oxidative Cleavage of Oximes and Derivatives with High-Valency Metals;358
1.8.7.4.3.4;26.1.6.4.3.4 Variation 4: Other Oxidative Cleavages of Oximes and Derivatives;361
1.8.7.4.4;26.1.6.4.4 Method 4: Nitrosative Cleavage of Oximes and Derivatives;362
1.8.7.4.5;26.1.6.4.5 Method 5: Reductive Cleavage of Oximes and Derivatives;363
1.8.7.4.5.1;26.1.6.4.5.1 Variation 1: Metal-Catalyzed Reductive Cleavage of Oximes and Derivatives;363
1.8.7.4.5.2;26.1.6.4.5.2 Variation 2: Other Reductive Cleavages of Oximes and Derivatives;365
1.8.7.5;26.1.6.5 Synthesis from Hydrazone Derivatives;365
1.8.7.5.1;26.1.6.5.1 Method 1: Hydrolysis of Hydrazone Derivatives;365
1.8.7.5.1.1;26.1.6.5.1.1 Variation 1: Acidic Hydrolysis of Hydrazones and Derivatives;366
1.8.7.5.1.2;26.1.6.5.1.2 Variation 2: Metal Salt Assisted Hydrolysis of Hydrazone Derivatives;366
1.8.7.5.2;26.1.6.5.2 Method 2: Cleavage of Hydrazone Derivatives by the Exchange Method;368
1.8.7.5.3;26.1.6.5.3 Method 3: Oxidative Cleavage of Hydrazone Derivatives;369
1.8.7.5.3.1;26.1.6.5.3.1 Variation 1: Aerobic Oxidation and Ozonolysis of Hydrazone Derivatives;369
1.8.7.5.3.2;26.1.6.5.3.2 Variation 2: Oxidative Cleavage of Hydrazone Derivatives with Peroxidic Compounds;370
1.8.7.5.3.3;26.1.6.5.3.3 Variation 3: Oxidative Cleavage of Hydrazone Derivatives with High-Valency Metals;372
1.8.7.5.3.4;26.1.6.5.3.4 Variation 4: Other Oxidative Cleavages of Hydrazone Derivatives;374
1.8.7.5.4;26.1.6.5.4 Method 4: Nitrosative Cleavage of Hydrazone Derivatives;376
1.8.7.5.5;26.1.6.5.5 Method 5: Reductive Cleavage of Hydrazone Derivatives;377
1.8.7.5.6;26.1.6.5.6 Method 6: Enzymatic Cleavage of Hydrazone Derivatives;377
1.8.7.6;26.1.6.6 Synthesis from O,O-Acetals;378
1.8.7.6.1;26.1.6.6.1 Method 1: Hydrolysis of O,O-Acetals;378
1.8.7.6.2;26.1.6.6.2 Method 2: Hydrolysis of O,O-Acetals by Exchange with Another Carbonyl Compound;380
1.8.7.6.3;26.1.6.6.3 Method 3: Metal-Induced Cleavage of O,O-Acetals;381
1.8.7.6.4;26.1.6.6.4 Method 4: Electrophilic Cleavage of O,O-Acetals;383
1.8.7.6.5;26.1.6.6.5 Method 5: Oxidative Cleavage of O,O-Acetals;384
1.8.7.6.6;26.1.6.6.6 Method 6: Reductive Cleavage of O,O-Acetals;385
1.8.7.6.7;26.1.6.6.7 Method 7: Nucleophilic Cleavage of O,O-Acetals;386
1.8.7.6.8;26.1.6.6.8 Method 8: Photolysis of O,O-Acetals;387
1.8.7.7;26.1.6.7 Synthesis from O,S-Acetals;388
1.8.7.7.1;26.1.6.7.1 Method 1: Hydrolysis of O,S-Acetals;388
1.8.7.7.2;26.1.6.7.2 Method 2: Cleavage of O,S-Acetals by Exchange with Another Carbonyl Compound;389
1.8.7.7.3;26.1.6.7.3 Method 3: Metal-Induced Cleavage of O,S-Acetals;389
1.8.7.7.4;26.1.6.7.4 Method 4: Oxidative Cleavage of O,S-Acetals;390
1.8.7.7.5;26.1.6.7.5 Method 5: Nitrosative Cleavage of O,S-Acetals;391
1.8.7.8;26.1.6.8 Synthesis from a-Hydroxylated Sulfones
;392
1.8.7.8.1;26.1.6.8.1 Method 1: Cleavage of a-Alkoxyalkylated Sulfones
;392
1.8.7.9;26.1.6.9 Synthesis from O,N-Acetals;393
1.8.7.9.1;26.1.6.9.1 Method 1: Hydrolysis of O,N-Acetals;393
1.8.7.9.2;26.1.6.9.2 Method 2: Reductive Cleavage of O,N-Acetals;394
1.8.7.10;26.1.6.10 Synthesis from a-Hydroxy and a-Trimethylsiloxy Alkylphosphonates
;395
1.8.7.10.1;26.1.6.10.1 Method 1: Deprotection of a-Hydroxy Alkylphosphonates
;395
1.8.7.11;26.1.6.11 Synthesis from S,S-Acetals;396
1.8.7.11.1;26.1.6.11.1 Method 1: Hydrolysis of S,S-Acetals;397
1.8.7.11.2;26.1.6.11.2 Method 2: Metal-Induced Cleavage of S,S-Acetals;397
1.8.7.11.3;26.1.6.11.3 Method 3: Alkylative and Electrophilic Cleavage of S,S-Acetals;399
1.8.7.11.4;26.1.6.11.4 Method 4: Oxidative Cleavage of S,S-Acetals;400
1.8.7.11.5;26.1.6.11.5 Method 5: Nitrosative Cleavage of S,S-Acetals;403
1.8.7.11.6;26.1.6.11.6 Method 6: Photolysis of S,S-Acetals;404
1.8.7.12;26.1.6.12 Synthesis from Dithioketal Monosulfoxides and Dithioketal Disulfoxides;404
1.8.7.12.1;26.1.6.12.1 Method 1: Hydrolysis of Dithioketal Monosulfoxides and Dithioketal Disulfoxides;404
1.8.7.12.2;26.1.6.12.2 Method 2: Metal-Catalyzed Cleavage of Dithioketal Monosulfoxides and Dithioketal Disulfoxides;405
1.8.7.13;26.1.6.13 Synthesis from S- or N-a-Substituted Sulfones
;406
1.8.7.13.1;26.1.6.13.1 Method 1: Acidic Hydrolysis of S- or N-a-Substituted Sulfones
;405
1.8.7.13.2;26.1.6.13.2 Method 2: Metal-Induced Hydrolyses of a-(Methylsulfanyl)methyl Sulfones
;407
1.8.7.14;26.1.6.14 Synthesis from 1-[(Methylsulfanyl)methyl]-1H-1,2,3-benzotriazoles, Dihydrobenzothiazoles, or Nitromethyl Sulfides;408
1.8.7.14.1;26.1.6.14.1 Method 1: Acidic Hydrolysis of 1-[(Methylsulfanyl)methyl]-1H-benzotriazoles;408
1.8.7.14.2;26.1.6.14.2 Method 2: Metal-Induced Hydrolysis of Dihydrobenzothiazoles;408
1.8.7.14.3;26.1.6.14.3 Method 3: Reductive Cleavage of Nitromethyl Sulfides;409
1.8.7.15;26.1.6.15 Synthesis from Diselenoacetals;410
1.8.7.15.1;26.1.6.15.1 Method 1: Metal-Induced Cleavage of Diselenoacetals;410
1.8.7.15.2;26.1.6.15.2 Method 2: Oxidative and Nitrosative Cleavage of Diselenoacetals;410
1.8.7.16;26.1.6.16 Synthesis from N,N-Acetals;411
1.8.7.16.1;26.1.6.16.1 Method 1: Hydrolysis of N,N-Acetals;411
1.8.7.17;26.1.6.17 Synthesis from a-Heterosubstituted Nitriles
;412
1.8.7.17.1;26.1.6.17.1 Method 1: Hydrolysis of a-Halogenated Nitriles
;412
1.8.7.17.2;26.1.6.17.2 Method 2: Hydrolysis of Cyanohydrins and Derivatives;413
1.8.7.17.2.1;26.1.6.17.2.1 Variation 1: Cleavage of O-Silylated Cyanohydrins;414
1.8.7.17.2.2;26.1.6.17.2.2 Variation 2: Hydrolysis of O-Acylated Cyanohydrins;415
1.8.7.17.3;26.1.6.17.3 Method 3: Hydrolysis of a-Cyanodithiocarbamates
;416
1.8.7.17.4;26.1.6.17.4 Method 4: Hydrolytic Cleavage of a-(Dialkylamino)nitriles
;417
1.8.7.18;26.1.6.18 Synthesis from Haloalkenes;417
1.8.7.18.1;26.1.6.18.1 Method 1: Acidic Hydrolysis of Haloalkenes;417
1.8.7.18.2;26.1.6.18.2 Method 2: Metal-Assisted Hydrolysis of Haloalkenes;419
1.8.7.19;26.1.6.19 Synthesis from Enol Derivatives;419
1.8.7.19.1;26.1.6.19.1 Method 1: Synthesis from Enol Ethers;419
1.8.7.19.2;26.1.6.19.2 Method 2: Hydrolysis of Enol Esters;420
1.8.7.19.3;26.1.6.19.3 Method 3: Synthesis from Silylated Enol Ethers;421
1.8.7.19.3.1;26.1.6.19.3.1 Variation 1: Miscellaneous Cleavages of Silylated Enol Ethers;422
1.8.7.19.3.2;26.1.6.19.3.2 Variation 2: Alkylation of Silylated Enol Ethers;423
1.8.7.19.4;26.1.6.19.4 Method 4: Alkylation of Stannylated Enols;424
1.8.7.19.5;26.1.6.19.5 Method 5: Hydrolysis of Enol Trifluoromethanesulfonates and Enol Phosphates;425
1.8.7.20;26.1.6.20 Synthesis from Vinyl Sulfides and Vinyl Selenides;426
1.8.7.20.1;26.1.6.20.1 Method 1: Hydrolysis of Vinyl Sulfides and Vinyl Selenides;427
1.8.7.20.2;26.1.6.20.2 Method 2: Metal-Catalyzed Hydrolysis of Vinyl Sulfides and Vinyl Selenides;427
1.8.7.21;26.1.6.21 Synthesis from Enamines and Derivatives;428
1.8.7.21.1;26.1.6.21.1 Method 1: Hydrolysis of Enamines and Derivatives;428
1.8.7.21.2;26.1.6.21.2 Method 2: Hydrolysis of Enamides;430
1.8.7.22;26.1.6.22 Synthesis from Nitroalkenes;431
1.8.7.22.1;26.1.6.22.1 Method 1: Reduction of Nitroalkenes;431
1.8.7.22.2;26.1.6.22.2 Method 2: Reductive Alkylation of Nitroalkenes;432
1.8.8;26.1.7 Synthesis by Addition;446
1.8.8.1;26.1.7.1 Method 1: Synthesis from Alkynes;446
1.8.8.1.1;26.1.7.1.1 Variation 1: By Mercury-Catalyzed Hydration;446
1.8.8.1.2;26.1.7.1.2 Variation 2: By Gold-Catalyzed Hydration;447
1.8.8.1.3;26.1.7.1.3 Variation 3: By Palladium-Catalyzed Hydration;448
1.8.8.1.4;26.1.7.1.4 Variation 4: By Platinum-Catalyzed Hydration;448
1.8.8.1.5;26.1.7.1.5 Variation 5: By Iron-Catalyzed Hydration;449
1.8.8.1.6;26.1.7.1.6 Variation 6: By Ruthenium-Catalyzed Hydration;449
1.8.8.1.7;26.1.7.1.7 Variation 7: By a Hydroboration--Oxidation Sequence;450
1.8.8.2;26.1.7.2 Method 2: Synthesis from Allenes;451
1.8.8.2.1;26.1.7.2.1 Variation 1: By Mercury-Catalyzed Hydration;451
1.8.8.2.2;26.1.7.2.2 Variation 2: By a Hydroboration--Oxidation Sequence;452
1.8.8.3;26.1.7.3 Method 3: Synthesis from Ketenes;452
1.8.8.3.1;26.1.7.3.1 Variation 1: With Organozinc Reagents;453
1.8.8.3.2;26.1.7.3.2 Variation 2: With Grignard Reagents;453
1.8.8.3.3;26.1.7.3.3 Variation 3: With Organolithium Reagents;454
1.8.9;26.1.8 Synthesis by Fragmentation and Rearrangement;458
1.8.9.1;26.1.8.1 Method 1: Fragmentation of Alkenes;458
1.8.9.2;26.1.8.2 Method 2: Fragmentation of 1,2-Diols;459
1.8.9.2.1;26.1.8.2.1 Variation 1: Fragmentation of 1,2-Diols with Periodates;459
1.8.9.2.2;26.1.8.2.2 Variation 2: Fragmentation of 1,2-Diols with Lead(IV) Acetate;460
1.8.9.2.3;26.1.8.2.3 Variation 3: Fragmentation of 1,2-Diols with N-Halosuccinimide;462
1.8.9.2.4;26.1.8.2.4 Variation 4: Miscellaneous Fragmentation Reactions of 1,2-Diols;463
1.8.9.3;26.1.8.3 Method 3: Fragmentation of 1,3-Diheterofunctionalized Compounds (Grob Fragmentation);464
1.8.9.3.1;26.1.8.3.1 Variation 1: Fragmentation of 1,3-Amino Halides, 1,3-Amino Sulfonates, and 1,3-Hydroxy Halides;465
1.8.9.3.2;26.1.8.3.2 Variation 2: Fragmentation of 1,3-Amino Alcohols;465
1.8.9.3.3;26.1.8.3.3 Variation 3: Fragmentation of Acyclic 1,3-Diols and Derivatives;466
1.8.9.3.4;26.1.8.3.4 Variation 4: Fragmentation of Cyclic 1,3-Diol Monosulfonates and Derivatives (Wharton Fragmentation);467
1.8.9.4;26.1.8.4 Method 4: Fragmentation of a,ß-Unsaturated Ketones (Eschenmoser Fragmentation)
;470
1.8.9.5;26.1.8.5 Method 5: Fragmentation of Ketones (Norrish Type II Fragmentation);473
1.8.9.6;26.1.8.6 Method 6: Electrocyclic Rearrangements;475
1.8.9.6.1;26.1.8.6.1 Variation 1: Claisen-Type Rearrangements;476
1.8.9.6.2;26.1.8.6.2 Variation 2: Oxy-Cope Rearrangement;478
1.8.9.7;26.1.8.7 Method 7: Isomerization of Allylic Alcohols;479
1.8.9.7.1;26.1.8.7.1 Variation 1: Metal-Promoted Isomerization;480
1.8.9.7.2;26.1.8.7.2 Variation 2: Tandem Isomerization--Aldol Reaction;482
1.8.9.7.3;26.1.8.7.3 Variation 3: Enantioselective Isomerization;483
1.8.9.7.4;26.1.8.7.4 Variation 4: Isomerization with Ring Expansion;484
1.8.9.8;26.1.8.8 Method 8: Rearrangement of 1,2-Diheterofunctionalized Compounds;485
1.8.9.8.1;26.1.8.8.1 Variation 1: 1,2-Diols and Derivatives;486
1.8.9.8.2;26.1.8.8.2 Variation 2: 2-Sulfanyl and 2-Selenyl Alcohol Derivatives;488
1.8.9.8.3;26.1.8.8.3 Variation 3: 2-Aza Alcohol Derivatives;489
1.8.9.8.4;26.1.8.8.4 Variation 4: 2-Halo Alcohols and Derivatives;490
1.8.9.8.5;26.1.8.8.5 Variation 5: 2-Hydroxy Ketones and Derivatives;493
1.8.9.8.6;26.1.8.8.6 Variation 6: 2-Epoxy Alcohols;494
1.8.9.9;26.1.8.9 Method 9: Rearrangement of Epoxides;496
1.8.9.9.1;26.1.8.9.1 Variation 1: Alkyl- and/or Aryl-Substituted Epoxides;496
1.8.9.9.2;26.1.8.9.2 Variation 2: a,ß-Epoxy Ketones
;499
1.8.9.9.3;26.1.8.9.3 Variation 3: Epoxysilanes;500
1.8.10;26.1.9 Synthesis from Other Ketones;508
1.8.10.1;26.1.9.1 Method 1: Monoalkylation of Lithium Enolates;509
1.8.10.1.1;26.1.9.1.1 Variation 1: Enantioselective Alkylation via Chiral Lithium Amide Deprotonation;515
1.8.10.2;26.1.9.2 Method 2: Monoalkylation of Sodium Enolates;516
1.8.10.3;26.1.9.3 Method 3: Monoalkylation of Potassium Enolates;518
1.8.10.4;26.1.9.4 Method 4: Palladium-Catalyzed Asymmetric Alkylations and Arylations of Alkali Ketone Enolates;520
1.8.10.5;26.1.9.5 Method 5: Monoalkylation of Magnesium Enolates;526
1.8.10.6;26.1.9.6 Method 6: Monoalkylation of Manganese Enolates;527
1.8.10.7;26.1.9.7 Method 7: Monoalkylation Using Sodium Triethylgermanate(II);529
1.8.10.8;26.1.9.8 Method 8: Miscellaneous Metal-Mediated Alkylations of Enolates;530
1.8.10.9;26.1.9.9 Method 9: Alkylation by Phase-Transfer Catalysis;532
1.8.10.10;26.1.9.10 Method 10: Free Radical Alkylation;534
1.8.10.11;26.1.9.11 Method 11: Polyalkylation of Enols and Enolates;538
1.8.10.12;26.1.9.12 Method 12: Isomerization by Carbonyl Transposition;542
1.8.10.13;26.1.9.13 Method 13: Epimerization via Enols and Enolates;543
1.8.10.14;26.1.9.14 Method 14: Deracemization by Enantioselective Protonation of Enolates;547
1.8.10.14.1;26.1.9.14.1 Variation 1: With a Chiral Proton Source;547
1.8.10.14.2;26.1.9.14.2 Variation 2: With an Achiral Proton Source under the Influence of a Chiral Ligand;550
1.8.10.14.3;26.1.9.14.3 Variation 3: Fungal Deracemization;551
1.8.10.15;26.1.9.15 Method 15: Norrish Type II Fragmentation;552
1.8.10.16;26.1.9.16 Method 16: Ring Expansion of Alicyclic Ketones;552
1.8.11;26.1.10 Synthesis from Enones by Formation of C--C Bonds;558
1.8.11.1;26.1.10.1 Method 1: By Addition of Organosilicon Reagents;558
1.8.11.2;26.1.10.2 Method 2: By Addition of Organostannane Reagents;560
1.8.11.3;26.1.10.3 Method 3: By Addition of Organoboron Reagents;561
1.8.11.4;26.1.10.4 Method 4: By Addition of Organoaluminum Reagents;564
1.8.11.5;26.1.10.5 Method 5: By Addition of Organozinc Reagents;565
1.8.11.6;26.1.10.6 Method 6: By Addition of Organocopper Reagents;570
1.8.11.7;26.1.10.7 Method 7: By Addition of Grignard Reagents;577
1.8.11.8;26.1.10.8 Method 8: By Michael and Michael-Type Addition Reactions;578
1.8.11.8.1;26.1.10.8.1 Variation 1: Organometallic Catalysis;578
1.8.11.8.2;26.1.10.8.2 Variation 2: Heterobimetallic Catalysis;582
1.8.11.8.3;26.1.10.8.3 Variation 3: Organocatalysis;586
1.8.11.8.4;26.1.10.8.4 Variation 4: Phase-Transfer Catalysis;589
1.8.11.8.5;26.1.10.8.5 Variation 5: Mukaiyama--Michael Reaction;592
1.8.11.9;26.1.10.9 Method 9: By the Sakurai--Hosomi Reaction;594
1.9;26.2 Product Class 2: Cyclobutanones and Their Precursors;602
1.9.1;26.2.1 Synthesis of Product Class 2;602
1.9.1.1;26.2.1.1 Method 1: Ring Formation by Cyclodialkylation of Protected Carbonyl Groups by 1,3-Dihalopropanes;602
1.9.1.1.1;26.2.1.1.1 Variation 1: From 1,3-Dithiane;602
1.9.1.1.2;26.2.1.1.2 Variation 2: From Methyl (Methylsulfanyl)methyl Sulfoxide;603
1.9.1.1.3;26.2.1.1.3 Variation 3: From Tosylmethyl Isocyanide;603
1.9.1.2;26.2.1.2 Method 2: Ring Formation by Cyclodialkylation of Ketones by 1,3-Dimetalated Propan-2-iminium Salts;604
1.9.1.3;26.2.1.3 Method 3: Cyclization by Intramolecular Substitution;604
1.9.1.3.1;26.2.1.3.1 Variation 1: Of a d-Halo Cyanohydrin
;604
1.9.1.3.2;26.2.1.3.2 Variation 2: Of O-Protected Alk-3-en-1-ols or Alk-3-yn-1-ols;604
1.9.1.4;26.2.1.4 Method 4: Ring Formation by Carbonylation;605
1.9.1.4.1;26.2.1.4.1 Variation 1: Of Titanacyclobutanes;606
1.9.1.4.2;26.2.1.4.2 Variation 2: Of (Alkoxyalkylidene)chromium Complexes;606
1.9.1.4.3;26.2.1.4.3 Variation 3: Of a Cobaltacyclopentan-2-one;607
1.9.1.5;26.2.1.5 Method 5: Reduction;607
1.9.1.5.1;26.2.1.5.1 Variation 1: Of 2-Acetoxycyclobutanones;607
1.9.1.5.2;26.2.1.5.2 Variation 2: Of 2,2-Dichlorocyclobutanones;608
1.9.1.6;26.2.1.6 Method 6: Oxidation;609
1.9.1.6.1;26.2.1.6.1 Variation 1: Of Cyclobutanols;609
1.9.1.6.2;26.2.1.6.2 Variation 2: Of Methylenecyclobutane;609
1.9.1.7;26.2.1.7 Method 7: Ring Formation by [2 + 2] Cycloaddition;609
1.9.1.7.1;26.2.1.7.1 Variation 1: Of Ketenes and Alkenes;610
1.9.1.7.2;26.2.1.7.2 Variation 2: Of Mono- or Dichloroketenes and Alkenes;612
1.9.1.7.3;26.2.1.7.3 Variation 3: Of Keteniminium Salts and Alkenes;613
1.9.1.7.4;26.2.1.7.4 Variation 4: Of Ketene Acetals and Acrylic or Maleic Acid Derivatives;615
1.9.1.7.5;26.2.1.7.5 Variation 5: Of Ketene Thioacetals and Alkenes;616
1.9.1.7.6;26.2.1.7.6 Variation 6: Of Ketene Silyl Acetals and Alkenes;617
1.9.1.7.7;26.2.1.7.7 Variation 7: Of N,N-Diethylprop-1-yn-1-amine and Alkenes;618
1.9.1.8;26.2.1.8 Method 8: Ring Enlargement of Cyclopropanones Formed by Addition of Diazomethane to Ketenes;619
1.9.1.9;26.2.1.9 Method 9: Ring Enlargement of the Cyclopropane Intermediate Formed by a Simmons--Smith Cyclopropanation Reaction;620
1.9.1.10;26.2.1.10 Method 10: Rearrangement of Spiro[2.2]pentanes;621
1.9.1.10.1;26.2.1.10.1 Variation 1: Of 1-Oxaspiro[2.2]pentanes;621
1.9.1.10.2;26.2.1.10.2 Variation 2: Of 1-Azaspiro[2.2]pentanes;624
1.9.1.11;26.2.1.11 Method 11: Rearrangement of (1-Hydroxyalkyl)cyclopropanes;625
1.9.1.11.1;26.2.1.11.1 Variation 1: Of 1-Alkoxy-1-(1-hydroxyalkyl)cyclopropanes;625
1.9.1.11.2;26.2.1.11.2 Variation 2: Of 1-(Arylsulfanyl)-1-(1-hydroxyalkyl)cyclopropanes;626
1.9.1.11.3;26.2.1.11.3 Variation 3: Of 1-(1-Hydroxyalkyl)-1-selanylcyclopropanes;628
1.9.1.11.4;26.2.1.11.4 Variation 4: Of 1-(1-Hydroxyalkyl)-1-(trimethylsilyl)cyclopropanes;629
1.9.1.11.5;26.2.1.11.5 Variation 5: Of (1-Formylamino)-1-(1-hydroxyalkyl)cyclopropanes;629
1.9.1.12;26.2.1.12 Method 12: Rearrangement of Cyclopropanol Derivatives;630
1.9.1.12.1;26.2.1.12.1 Variation 1: Of 1-Vinylcyclopropanols;630
1.9.1.12.2;26.2.1.12.2 Variation 2: Of 1-(1-Hydroxyalkyl)- or 1-Formylcyclopropanols;632
1.9.1.12.3;26.2.1.12.3 Variation 3: Of 1-(Aminomethyl)cyclopropanols;638
1.9.1.12.4;26.2.1.12.4 Variation 4: Of a Bicyclo[4.1.0]heptan-2-one Tosylhydrazone;639
1.9.1.13;26.2.1.13 Method 13: Rearrangement of (1-Bromoalkylidene)cyclopropanes;639
1.9.1.14;26.2.1.14 Method 14: Ring Contraction;640
1.9.1.14.1;26.2.1.14.1 Variation 1: Of .-Lactone Tosylhydrazones
;640
1.9.1.14.2;26.2.1.14.2 Variation 2: Of Cyclohex-2-enones;640
1.9.1.14.3;26.2.1.14.3 Variation 3: Of Cyclohex-3-enones;641
1.9.1.14.4;26.2.1.14.4 Variation 4: Of Cycloocta-2,4,6-trienones;641
1.9.1.15;26.2.1.15 Method 15: Preparation from Preformed Four-Membered Rings;642
1.9.1.15.1;26.2.1.15.1 Variation 1: From Cyclobutanones;642
1.9.1.15.2;26.2.1.15.2 Variation 2: From Cyclobutenones;645
1.9.1.15.3;26.2.1.15.3 Variation 3: From 1,2-Bis(trimethylsiloxy)cyclobutene;646
1.10;26.3 Product Class 3: Cyclopropanones and Their Precursors;652
1.10.1;26.3.1 Product Subclass 1: Cyclopropanones;652
1.10.1.1;26.3.1.1 Synthesis of Product Subclass 1;652
1.10.1.1.1;26.3.1.1.1 Method 1: Photolysis of Strained Rings;652
1.10.1.1.1.1;26.3.1.1.1.1 Variation 1: Photodecarbonylation of Cyclobutanediones;652
1.10.1.1.1.2;26.3.1.1.1.2 Variation 2: Photodenitrogenation of Dihydropyrazolones;653
1.10.1.1.2;26.3.1.1.2 Method 2: Ring-Closing Dehalogenation of a-Halo and a,a'-Dihalo Ketones;653
1.10.1.1.2.1;26.3.1.1.2.1 Variation 1: With Sterically Hindered Bases;653
1.10.1.1.2.2;26.3.1.1.2.2 Variation 2: Electrochemical Dehalogenation;654
1.10.1.1.2.3;26.3.1.1.2.3 Variation 3: Sodium Iodide Induced Dehalogenation;654
1.10.1.1.2.4;26.3.1.1.2.4 Variation 4: Carbonylmetalate-Induced Dehalogenation;655
1.10.1.1.3;26.3.1.1.3 Method 3: Addition of Diazoalkanes to Ketenes;655
1.10.1.1.4;26.3.1.1.4 Method 4: Isomerization of Allene Oxides;656
1.10.1.1.4.1;26.3.1.1.4.1 Variation 1: Thermal Isomerization;657
1.10.2;26.3.2 Product Subclass 2: Cyclopropanone Hemiacetals;657
1.10.2.1;26.3.2.1 Synthesis of Product Subclass 2;657
1.10.2.1.1;26.3.2.1.1 Method 1: Photodecarbonylation of Cyclobutanediones;657
1.10.2.1.2;26.3.2.1.2 Method 2: Ring-Closing Dehalogenation;658
1.10.2.1.2.1;26.3.2.1.2.1 Variation 1: Electroreduction of a,a'-Dihalo Ketones;658
1.10.2.1.2.2;26.3.2.1.2.2 Variation 2: Base-Induced Dehydrohalogenation of a-Halo Ketones;658
1.10.2.1.2.3;26.3.2.1.2.3 Variation 3: Sodium-Mediated Ring Closure of ß-Halo Esters;659
1.10.2.1.2.4;26.3.2.1.2.4 Variation 4: Sodium-Mediated Ring Closure of ß-Haloamides
;659
1.10.2.1.3;26.3.2.1.3 Method 3: Addition Reactions of Ketenes;660
1.10.2.1.3.1;26.3.2.1.3.1 Variation 1: Cyclopropanation of Silylketene Acetals;660
1.10.2.1.3.2;26.3.2.1.3.2 Variation 2: Cyclopropanation of 1-Alkoxyvinyl Esters;660
1.10.2.1.3.3;26.3.2.1.3.3 Variation 3: Addition of Glacial Acetic Acid to Cyclopropanones;661
1.10.3;26.3.3 Product Subclass 3: Cyclopropanone Hemiaminals;661
1.10.3.1;26.3.3.1 Synthesis of Product Subclass 3;661
1.10.3.1.1;26.3.3.1.1 Method 1: Addition of Amines to Cyclopropanone;661
1.10.4;26.3.4 Product Subclass 4: Cyclopropanone Acetals;662
1.10.4.1;26.3.4.1 Synthesis of Product Subclass 4;662
1.10.4.1.1;26.3.4.1.1 Method 1: Alcoholysis of 1'-Substituted Cyclopropyl Ethers
;662
1.10.4.1.1.1;26.3.4.1.1.1 Variation 1: From 1,1-Dihalocyclopropanes;663
1.10.4.1.2;26.3.4.1.2 Method 2: Reductive Cyclization of a,a'-Dihalopropanone Acetals
;663
1.10.4.1.3;26.3.4.1.3 Method 3: Addition of Carbenes or Carbenoids to Ketene Acetals;664
1.10.4.1.3.1;26.3.4.1.3.1 Variation 1: Addition of Dialkoxycarbenes to Ketones;665
1.10.4.1.4;26.3.4.1.4 Method 4: Addition to Cyclopropenone Acetals;666
1.10.4.1.5;26.3.4.1.5 Method 5: Ring Closure of (.,.-Dialkoxyallyl)zirconocenes
;667
1.10.4.1.6;26.3.4.1.6 Method 6: Photoisomerization of Dienedione Monoacetals;667
1.10.5;26.3.5 Product Subclass 5: Cyclopropane-1,1-diamines;668
1.10.5.1;26.3.5.1 Synthesis of Product Subclass 5;668
1.10.5.1.1;26.3.5.1.1 Method 1: Secondary Amine Induced Ring Closure of a-Halo Ketones
;668
1.10.5.1.2;26.3.5.1.2 Method 2: Amine Addition to Cyclopropanone;668
1.10.6;26.3.6 Product Subclass 6: Cyclopropane Thioacetals;669
1.10.6.1;26.3.6.1 Synthesis of Product Subclass 6;669
1.10.6.1.1;26.3.6.1.1 Method 1: Substitution of Cyclopropanone Derivatives;669
1.10.6.1.1.1;26.3.6.1.1.1 Variation 1: Using Basic Conditions;669
1.10.6.1.1.2;26.3.6.1.1.2 Variation 2: By Metalation;670
1.10.6.1.2;26.3.6.1.2 Method 2: Ring Closure of 1,1,3-Tris(phenylsulfanyl)alkanes;670
1.10.6.1.3;26.3.6.1.3 Method 3: Addition of Thiols to Cyclopropanones;671
1.10.7;26.3.7 Product Subclass 7: 1,1-Bis(seleno)cyclopropanes;671
1.10.7.1;26.3.7.1 Synthesis of Product Subclass 7;671
1.10.7.1.1;26.3.7.1.1 Method 1: Substitution of Cyclopropanone Derivatives;671
1.10.7.1.2;26.3.7.1.2 Method 2: Ring Closure of Seleno Derivatives;672
1.10.8;26.3.8 Product Subclass 8: Cyclopropenones;673
1.10.8.1;26.3.8.1 Synthesis of Product Subclass 8;673
1.10.8.1.1;26.3.8.1.1 Method 1: Hydrolysis;673
1.10.8.1.1.1;26.3.8.1.1.1 Variation 1: Of Cyclopropenone Acetals;673
1.10.8.1.1.2;26.3.8.1.1.2 Variation 2: Of Dichlorocyclopropenes;675
1.10.8.1.1.3;26.3.8.1.1.3 Variation 3: Of Cyclopropenylium Salts;675
1.10.8.1.2;26.3.8.1.2 Method 2: Oxidation of Cyclopropenes;676
1.10.8.1.3;26.3.8.1.3 Method 3: Photodecarbonylation of Cyclobutenediones;677
1.10.8.1.4;26.3.8.1.4 Method 4: Dehydrohalogenation of a,a'-Dihalo Ketones
;677
1.10.9;26.3.9 Product Subclass 9: Cyclopropyl Ketones and Cyclopropanecarbaldehydes;678
1.10.9.1;26.3.9.1 Synthesis of Product Subclass 9;678
1.10.9.1.1;26.3.9.1.1 Method 1: Ring-Closure Reactions;678
1.10.9.1.1.1;26.3.9.1.1.1 Variation 1: Of .-Chloro Ketones
;678
1.10.9.1.1.2;26.3.9.1.1.2 Variation 2: Of 4-Oxopentyl Phosphate Carbanions;679
1.10.9.1.1.3;26.3.9.1.1.3 Variation 3: Of Methyl 2,3-Dihalopropanoates;679
1.10.9.1.1.4;26.3.9.1.1.4 Variation 4: Of Oxoenolates;680
1.10.9.1.2;26.3.9.1.2 Method 2: Cyclization of Oxo Esters and Ketones with 1,2-Dibromoethane;680
1.10.9.1.3;26.3.9.1.3 Method 3: Addition Reactions;681
1.10.9.1.3.1;26.3.9.1.3.1 Variation 1: Of Carbenes to Undec-2-en-5-yn-1-ol;681
1.10.9.1.3.2;26.3.9.1.3.2 Variation 2: Of Diphenylsulfonium Isopropylide to Chiral Lactams;681
1.10.9.1.3.3;26.3.9.1.3.3 Variation 3: Of Diazocyclopropane to Aldehydes;683
1.10.9.1.4;26.3.9.1.4 Method 4: Oxidation Reactions;683
1.10.9.1.4.1;26.3.9.1.4.1 Variation 1: Swern Oxidation of Cyclopropylcarbinols;683
1.10.9.1.4.2;26.3.9.1.4.2 Variation 2: Oxidative Ring Opening;684
1.10.9.1.5;26.3.9.1.5 Method 5: Addition of Methyllithium to Cyclopropane Carboxylic Acids;685
1.10.9.1.6;26.3.9.1.6 Method 6: Rearrangement of Allene Oxides;685
1.10.9.1.7;26.3.9.1.7 Method 7: Photolysis of ß,.-Unsaturated Ketones
;686
1.11;26.4 Product Class 4: 1,2-Diketones and Related Compounds;692
1.11.1;26.4.1 Product Subclass 1: 1,2-Diketones;694
1.11.1.1;26.4.1.1 Synthesis of Product Subclass 1;694
1.11.1.1.1;26.4.1.1.1 Method 1: Coupling Reactions;694
1.11.1.1.1.1;26.4.1.1.1.1 Variation 1: Coupling of Aldehydes;695
1.11.1.1.1.2;26.4.1.1.1.2 Variation 2: Coupling of Carboxylic Acid Derivatives;696
1.11.1.1.1.3;26.4.1.1.1.3 Variation 3: Coupling of a-Oxonitriles
;701
1.11.1.1.1.4;26.4.1.1.1.4 Variation 4: Carbonylative Coupling of Alkyl Halides with Organometallic Reagents;703
1.11.1.1.1.5;26.4.1.1.1.5 Variation 5: Nucleophilic Acylation of Carboxylic Acid Derivatives by Acyllithium Reagents;705
1.11.1.1.1.6;26.4.1.1.1.6 Variation 6: Addition of Organometallic Reagents to 1,2-Diacyl Derivatives;707
1.11.1.1.1.7;26.4.1.1.1.7 Variation 7: Friedel--Crafts Acylation;710
1.11.1.1.2;26.4.1.1.2 Method 2: Substitution of Heteroatoms;712
1.11.1.1.2.1;26.4.1.1.2.1 Variation 1: Hydrolysis of a-Oxo Ketals
;712
1.11.1.1.2.2;26.4.1.1.2.2 Variation 2: Hydrolysis of a-Oxo Thioketals
;713
1.11.1.1.2.3;26.4.1.1.2.3 Variation 3: Hydrolysis of a-Oxo Imines
;715
1.11.1.1.2.4;26.4.1.1.2.4 Variation 4: Hydrolysis of a,a-Dihalo Ketones
;716
1.11.1.1.2.5;26.4.1.1.2.5 Variation 5: From a-Diazo Ketones
;717
1.11.1.1.3;26.4.1.1.3 Method 3: Oxidation;718
1.11.1.1.3.1;26.4.1.1.3.1 Variation 1: Of Ketones;718
1.11.1.1.3.2;26.4.1.1.3.2 Variation 2: Of Enones by Ozonolysis;720
1.11.1.1.3.3;26.4.1.1.3.3 Variation 3: Of a-Hydroxy Ketones
;721
1.11.1.1.3.4;26.4.1.1.3.4 Variation 4: Of 1,2-Diols;722
1.11.1.1.3.5;26.4.1.1.3.5 Variation 5: Of Alkenes;724
1.11.1.1.3.6;26.4.1.1.3.6 Variation 6: Of Alkynes;726
1.11.1.1.3.7;26.4.1.1.3.7 Variation 7: Of Arenes, Phenols, and Catechols;727
1.11.1.1.3.8;26.4.1.1.3.8 Variation 8: Of a-Oxo Phosphorus Ylides
;729
1.11.1.1.3.9;26.4.1.1.3.9 Variation 9: Of a-Bromo Ketones
;731
1.11.1.1.4;26.4.1.1.4 Method 4: Addition of Bromine to 1,2-Bis(siloxy)alkenes;732
1.11.1.1.5;26.4.1.1.5 Method 5: Rearrangements of a,ß-Epoxy Ketones
;733
1.11.1.1.6;26.4.1.1.6 Methods 6: Additional Methods;734
1.11.1.2;26.4.1.2 Applications of Product Subclass 1 in Organic Synthesis;736
1.11.1.2.1;26.4.1.2.1 Method 1: Oxidation of 1,2-Diketones to Carboxylic Acids;736
1.11.1.2.2;26.4.1.2.2 Method 2: Addition Reactions with 1,2-Diketones;737
1.11.1.2.2.1;26.4.1.2.2.1 Variation 1: Addition of Hydrogen;737
1.11.1.2.2.2;26.4.1.2.2.2 Variation 2: Addition of Organometallic Reagents;738
1.11.1.2.2.3;26.4.1.2.2.3 Variation 3: Addition of Carbon Functionalities;739
1.11.1.2.2.4;26.4.1.2.2.4 Variation 4: Addition of Heteroatoms;741
1.11.1.2.2.5;26.4.1.2.2.5 Variation 5: Cycloadditions of 1,2-Diketones;743
1.11.1.2.3;26.4.1.2.3 Method 3: Ring Contraction of Cyclic 1,2-Diketones;743
1.11.2;26.4.2 Product Subclass 2: a-Thioxo Ketones
;744
1.11.2.1;26.4.2.1 Synthesis of Product Subclass 2;744
1.11.2.1.1;26.4.2.1.1 Method 1: Substitution of Heteroatoms;744
1.11.2.1.1.1;26.4.2.1.1.1 Variation 1: In 1,2-Diketones;744
1.11.2.1.1.2;26.4.2.1.1.2 Variation 2: In a-Diazo Ketones
;745
1.11.2.1.2;26.4.2.1.2 Method 2: Oxidation of Active Methylene Compounds;746
1.11.2.1.2.1;26.4.2.1.2.1 Variation 1: Of Ketones;746
1.11.2.1.2.2;26.4.2.1.2.2 Variation 2: Of a-Sulfanyl Ketones
;747
1.11.2.1.3;26.4.2.1.3 Method 3: Addition;749
1.11.2.1.3.1;26.4.2.1.3.1 Variation 1: Of Thionyl Chloride to Silyl Enol Ethers;749
1.11.2.1.3.2;26.4.2.1.3.2 Variation 2: Of Sulfur Ylides to Carboxylic Acid Derivatives;749
1.11.2.1.4;26.4.2.1.4 Method 4: Rearrangements;750
1.11.2.1.4.1;26.4.2.1.4.1 Variation 1: Retro-Diels--Alder Reactions;750
1.11.2.1.4.2;26.4.2.1.4.2 Variation 2: Rearrangement of Thiirene or Thiirane S-Oxides;751
1.11.2.2;26.4.2.2 Applications of Product Subclass 2 in Organic Synthesis;752
1.11.3;26.4.3 Product Subclass 3: a-Selenoxo Ketones
;753
1.11.3.1;26.4.3.1 Synthesis of Product Subclass 3;753
1.11.3.1.1;26.4.3.1.1 Method 1: Substitution of Heteroatoms;753
1.11.3.1.1.1;26.4.3.1.1.1 Variation 1: In a-Diazo Ketones
;753
1.11.3.1.1.2;26.4.3.1.1.2 Variation 2: From a-Oxo Sulfonium Ylides
;754
1.11.3.1.2;26.4.3.1.2 Method 2: Oxidation of Active Methylene Compounds;755
1.11.3.1.3;26.4.3.1.3 Method 3: Addition of Selenoxides to Activated Alkynes;756
1.11.3.1.4;26.4.3.1.4 Methods 4: Additional Methods;757
1.11.3.2;26.4.3.2 Applications of Product Subclass 3 in Organic Synthesis;757
1.11.4;26.4.4 Product Subclass 4: a-Imino, a-Hydroxyimino, and a-Hydrazono Ketones
;758
1.11.4.1;26.4.4.1 Synthesis of Product Subclass 4;759
1.11.4.1.1;26.4.4.1.1 Method 1: Coupling Reactions between Carboxylic Acid Derivatives and Imine Derivatives;759
1.11.4.1.2;26.4.4.1.2 Method 2: Substitution of Heteroatoms in 1,2-Diketones;762
1.11.4.1.3;26.4.4.1.3 Method 3: Oxidation;763
1.11.4.1.3.1;26.4.4.1.3.1 Variation 1: Nitrosation of Ketones;763
1.11.4.1.3.2;26.4.4.1.3.2 Variation 2: Nitrosation of Enones;764
1.11.4.1.3.3;26.4.4.1.3.3 Variation 3: Nitrosation of Phenols;765
1.11.4.1.4;26.4.4.1.4 Method 4: From a-Hydroxyimino Ketones
;766
1.11.4.1.5;26.4.4.1.5 Methods 5: Additional Methods;767
1.11.4.2;26.4.4.2 Applications of Product Subclass 4 in Organic Synthesis;768
1.11.5;26.4.5 Product Subclass 5: a-Diazo Ketones
;769
1.11.5.1;26.4.5.1 Synthesis of Product Subclass 5;769
1.11.5.1.1;26.4.5.1.1 Method 1: Substitution;769
1.11.5.1.1.1;26.4.5.1.1.1 Variation 1: Of Acyl Halides;769
1.11.5.1.1.2;26.4.5.1.1.2 Variation 2: Of Hydrazones;770
1.11.5.1.2;26.4.5.1.2 Method 2: Oxidation;771
1.11.5.1.2.1;26.4.5.1.2.1 Variation 1: Diazo-Transfer Reactions with Active Methylene Compounds;771
1.11.5.1.2.2;26.4.5.1.2.2 Variation 2: Diazotization of Amines;773
1.11.5.1.3;26.4.5.1.3 Method 3: From a-Diazo Carbonyl Compounds
;774
1.11.5.2;26.4.5.2 Applications of Product Subclass 5 in Organic Synthesis;775
1.12;26.5 Product Class 5: a,a-Diheterosubstituted Ketones
;790
1.12.1;26.5.1 Product Subclass 1: a,a-Difluoro Ketones
;790
1.12.1.1;26.5.1.1 Synthesis of Product Subclass 1;790
1.12.1.1.1;26.5.1.1.1 Method 1: Direct Fluorination of Ketones;790
1.12.1.1.2;26.5.1.1.2 Method 2: Oxidation of a,a-Difluoro Alcohols
;791
1.12.1.1.3;26.5.1.1.3 Method 3: Synthesis from Difluoro Enoxysilanes;792
1.12.1.1.4;26.5.1.1.4 Method 4: Synthesis via Reformatsky-Type Aldol Reactions;794
1.12.1.1.5;26.5.1.1.5 Method 5: Synthesis from Lewis Acid Mediated Aldol-Type Reactions;795
1.12.1.1.6;26.5.1.1.6 Method 6: Synthesis from Anhydrides, Esters, or Amides and Organometallic Reagents;795
1.12.1.1.7;26.5.1.1.7 Method 7: Addition of Difluoroiodomethyl Ketones to Alkenes;797
1.12.1.1.8;26.5.1.1.8 Method 8: Synthesis from Alkynes;798
1.12.1.1.9;26.5.1.1.9 Method 9: Conversion of Arylperfluoroalkanes into Aryl Perfluoroalkyl Ketones;799
1.12.1.1.10;26.5.1.1.10 Method 10: Synthesis by Rearrangement;800
1.12.2;26.5.2 Product Subclass 2: a,a-Dichloro Ketones
;801
1.12.2.1;26.5.2.1 Synthesis of Product Subclass 2;802
1.12.2.1.1;26.5.2.1.1 Method 1: Synthesis by Direct Chlorination of Ketones;802
1.12.2.1.2;26.5.2.1.2 Method 2: Via Acylation Reactions;804
1.12.2.1.3;26.5.2.1.3 Method 3: By Addition of Organometallic Reagents;806
1.12.2.1.4;26.5.2.1.4 Method 4: Chlorination of Terminal Alkynes;806
1.12.2.1.5;26.5.2.1.5 Method 5: [2 + 2]-Cycloaddition Reactions of Dichloroketenes;807
1.12.2.1.6;26.5.2.1.6 Method 6: Intramolecular Insertion of Trichloromethyl Ketones into Alkenes, Catalyzed by Ruthenium Complexes;808
1.12.3;26.5.3 Product Subclass 3: a,a-Dibromo Ketones and a,a-Diiodo Ketones
;809
1.12.3.1;26.5.3.1 Synthesis of Product Subclass 3;809
1.12.3.1.1;26.5.3.1.1 Method 1: Synthesis of Dibromo Ketones by Direct Bromination of Ketones;809
1.12.3.1.2;26.5.3.1.2 Method 2: Synthesis of Diiodo Ketones by Direct Iodination of Ketones;812
1.12.3.1.3;26.5.3.1.3 Method 3: Synthesis from a-Diazo Ketones
;813
1.12.3.1.4;26.5.3.1.4 Method 4: Synthesis via a,a-Dibromo Anions
;814
1.12.3.1.5;26.5.3.1.5 Method 5: Synthesis from Alkynes;815
1.12.4;26.5.4 Product Subclass 4: a-Alkoxy-a-halo Ketones
;816
1.12.4.1;26.5.4.1 Synthesis of Product Subclass 4;817
1.12.4.1.1;26.5.4.1.1 Method 1: Fluorination of a-Alkoxy Ketones
;817
1.12.4.1.2;26.5.4.1.2 Method 2: Chlorination of a-Alkoxy Ketones
;817
1.12.4.1.3;26.5.4.1.3 Method 3: Bromination of a-Alkoxy Ketones
;818
1.12.4.1.4;26.5.4.1.4 Method 4: From a-Alkoxy- or a-Halo-a,ß-unsaturated Ketones
;820
1.12.4.1.5;26.5.4.1.5 Method 5: From a-Diazo Ketones;821
1.12.4.1.6;26.5.4.1.6 Method 6: By Addition of an Organometallic Group;821
1.12.4.1.7;26.5.4.1.7 Method 7: By Addition of Bromine to 1,2-Dialkoxyalkenes;822
1.12.5;26.5.5 Product Subclass 5: a-Halo-a-sulfanyl and a-Halo-a-sulfinyl Ketones
;823
1.12.5.1;26.5.5.1 Synthesis of Product Subclass 5;823
1.12.5.1.1;26.5.5.1.1 Method 1: Substitution of Hydrogen with Sulfur Reagents;823
1.12.5.1.2;26.5.5.1.2 Method 2: Halogenation of a-Sulfanyl Ketones
;824
1.12.5.1.3;26.5.5.1.3 Method 3: Oxidation of a-Chloro-a-sulfinyl Alcohols
;826
1.12.6;26.5.6 Product Subclass 6: a-Amino-a-halo and a-Halo-a-nitro Ketones
;826
1.12.6.1;26.5.6.1 Synthesis of Product Subclass 6;827
1.12.6.1.1;26.5.6.1.1 Method 1: Synthesis of a-Fluoro-a-nitro Ketones Using Perchloryl Fluoride
;827
1.12.6.1.2;26.5.6.1.2 Method 2: Chlorination of a-Amino Ketones
;827
1.12.6.1.3;26.5.6.1.3 Method 3: Oxidation of a-Chloro-a-nitro Alcohols
;828
1.12.6.1.4;26.5.6.1.4 Method 4: Synthesis from Trichloronitromethane;829
1.12.7;26.5.7 Product Subclass 7: a,a-Dialkoxy Ketones
;829
1.12.7.1;26.5.7.1 Synthesis of Product Subclass 7;830
1.12.7.1.1;26.5.7.1.1 Method 1: Synthesis of a,a-Dialkoxy Ketones from Ketones
;830
1.12.7.1.2;26.5.7.1.2 Method 2: Synthesis of a,a-Dialkoxy Ketones from a-Sulfinyl Ketones
;831
1.12.7.1.3;26.5.7.1.3 Method 3: Oxidation of a-Hydroxy Acetals
;831
1.12.7.1.3.1;26.5.7.1.3.1 Variation 1: Oxidation by Dess--Martin Periodinane;832
1.12.7.1.3.2;26.5.7.1.3.2 Variation 2: Swern Oxidation;832
1.12.7.1.3.3;26.5.7.1.3.3 Variation 3: Oxidation by Chromium(VI) Oxide;833
1.12.7.1.3.4;26.5.7.1.3.4 Variation 4: Oxidation by Ruthenium(IV) Oxide;834
1.12.7.1.4;26.5.7.1.4 Method 4: Oxidation of 2-Alkoxyphenols;834
1.12.7.1.5;26.5.7.1.5 Method 5: Synthesis from Anhydrides, Esters, or Amides and an Organometallic Reagent;835
1.12.7.1.5.1;26.5.7.1.5.1 Variation 1: Synthesis from Functional Anhydrides, Esters, Nitriles, or Amides;835
1.12.7.1.5.2;26.5.7.1.5.2 Variation 2: Synthesis from Dialkoxymethyllithium Reagents;836
1.12.7.1.6;26.5.7.1.6 Method 6: Synthesis from a-Diazo Ketones
;837
1.12.7.1.7;26.5.7.1.7 Method 7: Synthesis of Dialkoxycyclobutanones via [2 + 2]-Cycloaddition Reactions;838
1.12.7.1.8;26.5.7.1.8 Method 8: Synthesis by Insertion of a Dialkoxycarbene into Strained Cyclic Ketones;838
1.12.7.1.9;26.5.7.1.9 Method 9: Synthesis by Acetalization of 1,2-Diketones or 1,2-Oxoaldehydes;839
1.12.7.1.10;26.5.7.1.10 Method 10: Synthesis by Rearrangement of a,a'-Dialkoxy Ketones
;840
1.12.7.1.11;26.5.7.1.11 Method 11: Synthesis from Reagents Derived from a,a-Dialkoxy Ketones
;840
1.12.7.1.11.1;26.5.7.1.11.1 Variation 1: Reactions of Enolates Derived from Dialkoxy Ketones;840
1.12.7.1.11.2;26.5.7.1.11.2 Variation 2: By Wittig Reaction;841
1.12.7.2;26.5.7.2 Applications of Product Subclass 7 in Organic Synthesis;842
1.12.7.2.1;26.5.7.2.1 Method 1: Stereoselective Applications;842
1.12.8;26.5.8 Product Subclass 8: a-Oxy-a-sulfanyl Ketones
;843
1.12.8.1;26.5.8.1 Synthesis of Product Subclass 8;844
1.12.8.1.1;26.5.8.1.1 Method 1: By Oxidation of ß-Oxo Sulfides
;844
1.12.8.1.2;26.5.8.1.2 Method 2: From a-Oxo Sulfoxides: Pummerer Reaction
;845
1.12.8.1.2.1;26.5.8.1.2.1 Variation 1: Synthesis of a-Acetoxy-ß-oxo Sulfides
;846
1.12.8.1.2.2;26.5.8.1.2.2 Variation 2: Synthesis of a-Siloxy-ß-oxo Sulfides;847
1.12.8.1.3;26.5.8.1.3 Method 3: By Oxidation of Functional Secondary Alcohols;847
1.12.8.1.3.1;26.5.8.1.3.1 Variation 1: By Swern Oxidation;848
1.12.8.1.3.2;26.5.8.1.3.2 Variation 2: Using Pyridinium Dichromate or Pyridinium Chlorochromate;848
1.12.8.1.4;26.5.8.1.4 Method 4: Synthesis from a-Halo-a-sulfanyl- or a-Halo-a-oxo Ketones
;849
1.12.8.1.5;26.5.8.1.5 Method 5: Synthesis from a-Diazo-ß-oxo Sulfones
;850
1.12.8.1.6;26.5.8.1.6 Method 6: Synthesis from Anhydrides, Esters, or Amides and an Organometallic Reagent;851
1.12.8.1.7;26.5.8.1.7 Method 7: Synthesis from a-Oxoaldehydes or 1,2-Diketones
;854
1.12.8.1.8;26.5.8.1.8 Method 8: Epoxidation of a-Sulfanyl-a,ß-unsaturated Ketones
;855
1.12.8.1.9;26.5.8.1.9 Method 9: Synthesis by Rearrangement;857
1.12.8.2;26.5.8.2 Applications of Product Subclass 8 in Organic Synthesis;857
1.12.9;26.5.9 Product Subclass 9: a-Alkoxy-a-seleno Ketones
;858
1.12.9.1;26.5.9.1 Synthesis of Product Subclass 9;859
1.12.9.1.1;26.5.9.1.1 Method 1: Synthesis from a-Seleno Ketones
;859
1.12.9.1.2;26.5.9.1.2 Method 2: Synthesis from a-Diazo Ketones
;860
1.12.10;26.5.10 Product Subclass 10: a-Alkoxy-a-amino and a-Amino-a-hydroxy Ketones
;861
1.12.10.1;26.5.10.1 Synthesis of Product Subclass 10;862
1.12.10.1.1;26.5.10.1.1 Method 1: By Oxidation of a-Amino Ketones
;862
1.12.10.1.2;26.5.10.1.2 Method 2: By Oxidation of a-Hydroxy N,O-Acetals
;863
1.12.10.1.3;26.5.10.1.3 Method 3: By Substitution of Heteroatoms;865
1.12.10.1.3.1;26.5.10.1.3.1 Variation 1: From a,a-Dihydroxy Ketones
;865
1.12.10.1.3.2;26.5.10.1.3.2 Variation 2: From a-Alkoxy-a-halo Ketones
;866
1.12.10.1.3.3;26.5.10.1.3.3 Variation 3: From a-Amino-a-halo Ketones
;867
1.12.10.1.4;26.5.10.1.4 Method 4: From a-Diazo Ketones
;868
1.12.10.1.5;26.5.10.1.5 Method 5: By Addition of Organometallic Reagents;869
1.12.10.1.5.1;26.5.10.1.5.1 Variation 1: From Functionalized Esters, Nitriles, or Amides;869
1.12.10.1.5.2;26.5.10.1.5.2 Variation 2: From a-Lithio N,O-Acetal Reagents
;870
1.12.10.1.6;26.5.10.1.6 Method 6: [3 + 2] Cycloaddition to Cyclopropenone;871
1.12.10.1.7;26.5.10.1.7 Method 7: Epoxidation of a,ß-Unsaturated ß-Amino Ketones
;871
1.12.10.1.8;26.5.10.1.8 Method 8: By Addition of Alcohols or Amines;872
1.12.10.1.8.1;26.5.10.1.8.1 Variation 1: Addition of Alcohols to 1,2-Oxoimines or 1,2-Oxoenamines;872
1.12.10.1.8.2;26.5.10.1.8.2 Variation 2: Addition of Amines to 1,2-Diketones;873
1.12.10.1.9;26.5.10.1.9 Method 9: By Cycloaddition;874
1.12.11;26.5.11 Product Subclass 11: a,a-Disulfanyl Ketones
;875
1.12.11.1;26.5.11.1 Synthesis of Product Subclass 11;876
1.12.11.1.1;26.5.11.1.1 Method 1: Substitution of Hydrogen with Sulfur Reagents;876
1.12.11.1.2;26.5.11.1.2 Method 2: From a-Oxo Sulfoxides
;878
1.12.11.1.3;26.5.11.1.3 Method 3: Oxidation of a-Hydroxy-1,3-dithianes
;878
1.12.11.1.4;26.5.11.1.4 Method 4: By Addition of Organometallic Reagents;879
1.12.11.1.5;26.5.11.1.5 Method 5: [2 + 2]-Cycloaddition Reactions of Disulfanyl Ketenes;881
1.12.11.1.6;26.5.11.1.6 Method 6: [3 + 2]-Cycloaddition Reactions from a-Oxo Dithioesters
;881
1.12.11.1.7;26.5.11.1.7 Method 7: By Addition of Dithiols to 1,2-Diketones;882
1.12.11.1.8;26.5.11.1.8 Method 8: By Rearrangement;883
1.12.11.1.9;26.5.11.1.9 Method 9: Synthesis with Retention of the Functional Group;884
1.12.11.1.9.1;26.5.11.1.9.1 Variation 1: Oxidation of a-Oxo Dithianes
;884
1.12.11.1.9.2;26.5.11.1.9.2 Variation 2: Alkylation of Enolates Bearing a-Dithianes
;885
1.12.11.1.9.3;26.5.11.1.9.3 Variation 3: Enolates Bearing a-Dithiane Sulfoxides
;886
1.12.12;26.5.12 Product Subclass 12: a-Amino-a-sulfanyl Ketones
;887
1.12.12.1;26.5.12.1 Synthesis of Product Subclass 12;887
1.12.12.1.1;26.5.12.1.1 Method 1: Via Pummerer Reaction from a-Sulfoxy Ketones
;887
1.12.12.1.2;26.5.12.1.2 Method 2: By Sulfanylation of a-Amino Ketones
;888
1.12.12.1.3;26.5.12.1.3 Method 3: From a-Alkylsulfanyl Ketones
;889
1.12.12.1.4;26.5.12.1.4 Method 4: By Substitution of Heteroatoms;889
1.12.12.1.4.1;26.5.12.1.4.1 Variation 1: From a-Amino-a-halo Ketones or Dihydroxy Ketones
;889
1.12.12.1.4.2;26.5.12.1.4.2 Variation 2: From a,a-Diamino Ketones
;890
1.12.12.1.4.3;26.5.12.1.4.3 Variation 3: From a-Diazo Ketones
;891
1.12.12.1.5;26.5.12.1.5 Method 5: Using a-Amino-a-(sulfonylmethyl)lithium Reagents
;891
1.12.12.1.6;26.5.12.1.6 Method 6: From 1,2-Diketones or 1,2-Oxoaldehydes;892
1.12.13;26.5.13 Product Subclass 13: a,a-Diselanyl Ketones
;893
1.12.13.1;26.5.13.1 Synthesis of Product Subclass 13;894
1.12.13.1.1;26.5.13.1.1 Method 1: By Addition of Metal Enolates to Elemental Selenium;894
1.12.13.1.2;26.5.13.1.2 Method 2: From a-Selanyl Ketones
;895
1.12.13.1.3;26.5.13.1.3 Method 3: From a-Diazo Ketones
;895
1.12.14;26.5.14 Product Subclass 14: a,a-Diamino Ketones
;896
1.12.14.1;26.5.14.1 Synthesis of Product Subclass 14;896
1.12.14.1.1;26.5.14.1.1 Method 1: By Substitution of Halogen;896
1.12.14.1.2;26.5.14.1.2 Method 2: Via Cycloaddition;897
1.12.14.1.3;26.5.14.1.3 Method 3: By Addition of Diaminoalkylmetal Reagents;898
1.12.14.1.4;26.5.14.1.4 Method 4: From 1,2-Diketones or a-Oxoaldehydes
;899
1.13;26.6 Product Class 6: a-Heterosubstituted Ketones
;914
1.13.1;26.6.1 Product Subclass 1: a-Fluoro Ketones
;914
1.13.1.1;26.6.1.1 Synthesis of Product Subclass 1;915
1.13.1.1.1;26.6.1.1.1 Method 1: Substitution of a Hydrogen Atom from an Alkanone;915
1.13.1.1.1.1;26.6.1.1.1.1 Variation 1: Direct Fluorination of Ketones without a Base;915
1.13.1.1.1.2;26.6.1.1.1.2 Variation 2: Deprotonation with an External Base;916
1.13.1.1.1.3;26.6.1.1.1.3 Variation 3: From an Alkanone via a Preformed Acetate Enol Ether;917
1.13.1.1.1.4;26.6.1.1.1.4 Variation 4: From Alkanones through Preformed Enol Silyl Ethers;918
1.13.1.1.1.5;26.6.1.1.1.5 Variation 5: Via a Preformed Enamine or Enamide;919
1.13.1.1.2;26.6.1.1.2 Method 2: Synthesis from Trifluoromethyl Ketones via Fluorinated Silyl Enol Ethers;921
1.13.2;26.6.2 Product Subclass 2: a-Chloro Ketones
;922
1.13.2.1;26.6.2.1 Synthesis of Product Subclass 2;923
1.13.2.1.1;26.6.2.1.1 Method 1: Substitution of a Hydrogen Atom from an Alkanone;923
1.13.2.1.1.1;26.6.2.1.1.1 Variation 1: Direct Chlorination with Chlorine;923
1.13.2.1.1.2;26.6.2.1.1.2 Variation 2: Direct Chlorination with Sulfuryl Chloride;926
1.13.2.1.1.3;26.6.2.1.1.3 Variation 3: Direct Chlorination with Selenium Oxychloride;928
1.13.2.1.1.4;26.6.2.1.1.4 Variation 4: Direct Chlorination with Sodium Chlorite/Manganese(III) Acetylacetonate;929
1.13.2.1.1.5;26.6.2.1.1.5 Variation 5: Direct Chlorination with Manganese(IV) Chloride;929
1.13.2.1.1.6;26.6.2.1.1.6 Variation 6: Direct Chlorination with Chlorotrimethylsilane/Dimethyl Sulfoxide;930
1.13.2.1.1.7;26.6.2.1.1.7 Variation 7: Direct Chlorination with Copper(II) Chloride/Lithium Chloride;931
1.13.2.1.1.8;26.6.2.1.1.8 Variation 8: Direct Chlorination with Trichloroisocyanuric Acid;933
1.13.2.1.1.9;26.6.2.1.1.9 Variation 9: Direct Chlorination with Hydrogen Chloride and Potassium Permanganate;933
1.13.2.1.1.10;26.6.2.1.1.10 Variation 10: Deprotonation with a Base Prior to Chlorination;934
1.13.2.1.1.11;26.6.2.1.1.11 Variation 11: Via a Preformed Enamine;935
1.13.2.1.1.12;26.6.2.1.1.12 Variation 12: Via a Preformed Silyl Enol Ether;937
1.13.2.1.1.13;26.6.2.1.1.13 Variation 13: Via a Preformed Enol Ether or Enol Ester;939
1.13.2.1.2;26.6.2.1.2 Method 2: Synthesis from a,a-Dichloro Ketones by Reduction
;940
1.13.2.1.3;26.6.2.1.3 Method 3: Synthesis by Oxidative Addition to an Alkene;943
1.13.2.1.3.1;26.6.2.1.3.1 Variation 1: Oxidation of an Alkene with Nitrosyl Chloride;943
1.13.2.1.3.2;26.6.2.1.3.2 Variation 2: Oxidation of an Alkene with Chromyl Chloride;945
1.13.2.1.3.3;26.6.2.1.3.3 Variation 3: Oxidation of an Alkene with 2-Cyanopyridinium Chlorochromate;946
1.13.2.1.3.4;26.6.2.1.3.4 Variation 4: Oxidation of an Alkene with Chromium(VI) Oxide and Chlorotrimethylsilane;946
1.13.2.1.3.5;26.6.2.1.3.5 Variation 5: Oxidation of an Alkene with Iron(III) Chloride;947
1.13.2.1.4;26.6.2.1.4 Method 4: Synthesis via the Opening of an Epoxide;948
1.13.2.1.4.1;26.6.2.1.4.1 Variation 1: Ring Opening of Epoxides with Chloro(dimethyl)sulfonium Chloride;949
1.13.2.1.4.2;26.6.2.1.4.2 Variation 2: Opening of an a,ß-Epoxy Ketone with Benzoyl Chloride
;949
1.13.3;26.6.3 Product Subclass 3: a-Bromo Ketones
;950
1.13.3.1;26.6.3.1 Synthesis of Product Subclass 3;951
1.13.3.1.1;26.6.3.1.1 Method 1: Substitution of Hydrogen by Bromine;951
1.13.3.1.1.1;26.6.3.1.1.1 Variation 1: Direct Bromination with Bromine in Acetic Acid/Water or in the Presence of Urea;951
1.13.3.1.1.2;26.6.3.1.1.2 Variation 2: Direct Bromination with Bromine in Concentrated Sulfuric Acid;953
1.13.3.1.1.3;26.6.3.1.1.3 Variation 3: Direct Bromination with Bromine in Methanol or Carbon Tetrachloride;953
1.13.3.1.1.4;26.6.3.1.1.4 Variation 4: Direct Bromination with Bromine in the Presence of Potassium Chlorate or Sodium Chlorate in Water;955
1.13.3.1.1.5;26.6.3.1.1.5 Variation 5: Bromination of an Enolate with Bromine;956
1.13.3.1.1.6;26.6.3.1.1.6 Variation 6: Bromination with Perbromide Salts;956
1.13.3.1.1.7;26.6.3.1.1.7 Variation 7: Bromination with Copper Bromide;958
1.13.3.1.1.8;26.6.3.1.1.8 Variation 8: Bromination with Bromine Donors in Dimethyl Sulfoxide;958
1.13.3.1.1.9;26.6.3.1.1.9 Variation 9: Bromination with Bromine Donors: Perfluoroalkanesulfonyl Bromides or Benzeneselenenyl Bromide;960
1.13.3.1.1.10;26.6.3.1.1.10 Variation 10: Bromination with Bromine Donors: Hexabromocyclopentadiene and Bromomalonic Derivatives;961
1.13.3.1.1.11;26.6.3.1.1.11 Variation 11: Bromination with Bromine Donors: N-Bromosuccinimide in the Presence of Ammonium Acetate;962
1.13.3.1.1.12;26.6.3.1.1.12 Variation 12: Bromination in the Presence of an Oxidant;963
1.13.3.1.2;26.6.3.1.2 Method 2: Synthesis from an Enol Ether;964
1.13.3.1.3;26.6.3.1.3 Method 3: Synthesis from an a,ß-Unsaturated Ketone by Reductive Bromination
;965
1.13.3.1.4;26.6.3.1.4 Method 4: Synthesis via the Ring Opening of an Epoxide;966
1.13.3.1.4.1;26.6.3.1.4.1 Variation 1: Photocatalytic Bromination of an Epoxide;966
1.13.3.1.4.2;26.6.3.1.4.2 Variation 2: Opening of an Epoxide with Bromo(dimethyl)sulfonium Bromide;967
1.13.3.1.5;26.6.3.1.5 Methods 5: Additional Methods;967
1.13.4;26.6.4 Product Subclass 4: a-Iodo Ketones
;968
1.13.4.1;26.6.4.1 Synthesis of Product Subclass 4;968
1.13.4.1.1;26.6.4.1.1 Method 1: Substitution of Hydrogen by Iodine;968
1.13.4.1.1.1;26.6.4.1.1.1 Variation 1: Direct Iodination under Acidic Conditions;969
1.13.4.1.1.2;26.6.4.1.1.2 Variation 2: Iodination of Enolates;970
1.13.4.1.2;26.6.4.1.2 Method 2: Synthesis by Conjugate Addition to a
-Iodocycloalkenones;972
1.13.4.1.3;26.6.4.1.3 Method 3: Synthesis from an Enol Ether by Enol Acetate;972
1.13.4.1.3.1;26.6.4.1.3.1 Variation 1: Via an Iodonium Ion Transfer Reagent and an Enol Acetate;972
1.13.4.1.3.2;26.6.4.1.3.2 Variation 2: Via an Iodonium Ion Transfer from the Reagent to a Silyl Enol Ether;974
1.13.4.1.4;26.6.4.1.4 Method 4: Synthesis via the Ring Opening of an Epoxide;975
1.13.4.1.4.1;26.6.4.1.4.1 Variation 1: Using Iodotrimethylsilane;975
1.13.4.1.4.2;26.6.4.1.4.2 Variation 2: Via the Ring Opening of an a-Nitro Epoxide ;976
1.13.4.1.5;26.6.4.1.5 Method 5: Synthesis via Oxidative Addition to an Alkene;976
1.13.4.1.5.1;26.6.4.1.5.1 Variation 1: Using Silver Chromate and Iodine;977
1.13.4.1.5.2;26.6.4.1.5.2 Variation 2: Using Pyridinium Dichromate and Iodine;977
1.13.4.1.5.3;26.6.4.1.5.3 Variation 3: Using Bis(2,4,6-trimethylpyridine)iodonium(I) Tetrafluoroborate/Dimethyl Sulfoxide;978
1.13.5;26.6.5 Product Subclass 5: a-Hydroxy and a-Oxo Ketones
;979
1.13.5.1;26.6.5.1 Synthesis of Product Subclass 5;979
1.13.5.1.1;26.6.5.1.1 Method 1: Substitution of an a-Hydrogen Atom
;979
1.13.5.1.1.1;26.6.5.1.1.1 Variation 1: From Alkanones by Deprotonation/Oxidation;979
1.13.5.1.1.2;26.6.5.1.1.2 Variation 2: By Oxidation with Dimethyldioxirane or an Oxaziridine;980
1.13.5.1.1.3;26.6.5.1.1.3 Variation 3: By Oxidation of a Titanium Enolate;981
1.13.5.1.1.4;26.6.5.1.1.4 Variation 4: By Reaction of a Tin Enolate with Nitrosobenzene;982
1.13.5.1.1.5;26.6.5.1.1.5 Variation 5: By Oxidation with a Molybdenum Complex;983
1.13.5.1.1.6;26.6.5.1.1.6 Variation 6: By Oxidation with Thallium(III) Salts;984
1.13.5.1.1.7;26.6.5.1.1.7 Variation 7: By Oxidation with Hydroxy(mesyloxy)iodobenzene;984
1.13.5.1.1.8;26.6.5.1.1.8 Variation 8: By Treatment with Oxygen and Triethyl Phosphite;985
1.13.5.1.2;26.6.5.1.2 Method 2: Synthesis via a Silyl Enol Ether;986
1.13.5.1.2.1;26.6.5.1.2.1 Variation 1: Oxidation with 3-Chloroperoxybenzoic Acid;986
1.13.5.1.2.2;26.6.5.1.2.2 Variation 2: Oxidation with Osmium(VIII) Oxide/4-Methylmorpholine N-Oxide;987
1.13.5.1.3;26.6.5.1.3 Method 3: Synthesis via Oxidative Addition to an Alkene;987
1.13.5.1.3.1;26.6.5.1.3.1 Variation 1: By Oxidation with Permanganate Salts;987
1.13.5.1.3.2;26.6.5.1.3.2 Variation 2: By Oxidation with Ruthenium(III) Chloride and Peracetic Acid;988
1.13.6;26.6.6 Product Subclass 6: a-Sulfanyl Ketones
;989
1.13.6.1;26.6.6.1 Synthesis of Product Subclass 6;990
1.13.6.1.1;26.6.6.1.1 Method 1: Substitution of a Hydrogen Atom;990
1.13.6.1.2;26.6.6.1.2 Method 2: a-Sulfanylation of Silyl Enol Ethers or Enamines
;991
1.13.6.1.3;26.6.6.1.3 Method 3: Regioselective a-Sulfanylation of Boryl Enol Ethers
;991
1.13.7;26.6.7 Product Subclass 7: a-Selanyl Ketones
;992
1.13.7.1;26.6.7.1 Synthesis of Product Subclass 7;992
1.13.7.1.1;26.6.7.1.1 Method 1: Substitution of a Hydrogen Atom;992
1.13.7.1.1.1;26.6.7.1.1.1 Variation 1: Selanylation under Neutral Conditions;992
1.13.7.1.1.2;26.6.7.1.1.2 Variation 2: Selanylation under Basic Conditions;994
1.13.7.1.1.3;26.6.7.1.1.3 Variation 3: Selanylation under Acidic Conditions;995
1.13.7.1.2;26.6.7.1.2 Method 2: Regioselective a-Selanylation of O-Silylated Enols or Boryl Enol Ethers
;997
1.13.7.1.3;26.6.7.1.3 Method 3: Synthesis by Homologation from Phenylselenoacetaldehyde;997
1.13.8;26.6.8 Product Subclass 8: a-Amino Ketones
;998
1.13.8.1;26.6.8.1 Synthesis of Product Subclass 8;999
1.13.8.1.1;26.6.8.1.1 Method 1: Neber Rearrangement;999
1.13.8.1.2;26.6.8.1.2 Method 2: Synthesis from Silyl Enol Ethers by Aminohydroxylation;1000
1.13.8.1.3;26.6.8.1.3 Method 3: Synthesis from a-Bromo Ketones by Substitution;1001
1.13.8.1.4;26.6.8.1.4 Method 4: Synthesis from Aldehydes and Iminium Salts;1002
1.13.8.1.5;26.6.8.1.5 Method 5: Synthesis from a-Amino Acids via an Oxazolidin-5-one;1003
1.13.8.1.6;26.6.8.1.6 Method 6: Synthesis via the Cyclization of an a-Amino Ester;1003
1.13.8.1.7;26.6.8.1.7 Method 7: Synthesis via the Electroreductive Coupling of Aliphatic Amides;1004
1.13.8.1.8;26.6.8.1.8 Method 8: Synthesis via the Selective Reduction of Acyl Cyanides;1004
1.13.8.1.9;26.6.8.1.9 Method 9: Synthesis from Amines;1005
1.13.9;26.6.9 Product Subclass 9: a-Phosphino and a-Phosphoryl Ketones;1006
1.13.9.1;26.6.9.1 Synthesis of Product Subclass 9;1006
1.13.9.1.1;26.6.9.1.1 Method 1: 2-(Diphenylphosphoryl)cycloalkanones by Base-Mediated Phosphinylation/Oxidation of Cycloalkanones;1006
1.13.9.1.2;26.6.9.1.2 Method 2: a-(Dialkoxyphosphoryl) Ketones by Rearrangement of a Vinyl Phosphate;1007
1.13.9.1.3;26.6.9.1.3 Method 3: Diethyl (2-Oxoethyl)phosphonates from a-Bromo Ketones and Diethyl Chlorophosphate
;1008
1.13.9.1.4;26.6.9.1.4 Method 4: a-Phosphorylated Ketones from a-Chloro Ketones
;1009
1.14;26.7 Product Class 7: Ynones;1016
1.14.1;26.7.1 Product Subclass 1: Propargyl Ketones;1016
1.14.1.1;26.7.1.1 Synthesis of Product Subclass 1;1016
1.14.1.1.1;26.7.1.1.1 Method 1: Acylation of Organometallic Reagents;1016
1.14.1.1.1.1;26.7.1.1.1.1 Variation 1: Acylation of Lithiated Alkynes with Carbonyl Compounds;1017
1.14.1.1.1.2;26.7.1.1.1.2 Variation 2: Copper(I)-Catalyzed Coupling of Terminal Alkynes and Acid Chlorides;1018
1.14.1.1.1.3;26.7.1.1.1.3 Variation 3: Coupling of Terminal Alkynes and Acid Chlorides under Bimetallic Copper(I)/Palladium Conditions;1018
1.14.1.1.1.4;26.7.1.1.1.4 Variation 4: Palladium(0)-Catalyzed Coupling of Trialkynylindiums with Acid Chlorides;1019
1.14.1.1.1.5;26.7.1.1.1.5 Variation 5: By Acylation of an Organometallic Reagent with a Propargylic Ester;1020
1.14.1.1.2;26.7.1.1.2 Method 2: Oxidation of Propargyl Alcohols;1020
1.14.1.1.2.1;26.7.1.1.2.1 Variation 1: By Propargylic Oxidation of Alkynes;1021
1.14.1.1.3;26.7.1.1.3 Method 3: Three-Component Couplings Involving Carbon Monoxide;1022
1.14.1.1.4;26.7.1.1.4 Method 4: By Elimination of Aminoalkenones;1022
1.14.1.1.5;26.7.1.1.5 Method 5: By Oxy-Cope Rearrangement;1023
1.14.1.1.6;26.7.1.1.6 Method 6: By Elimination of a,.-Dioxo Phosphonium Ylides
;1023
1.14.2;26.7.2 Product Subclass 2: ß,.-Alkynyl Ketones
;1024
1.14.2.1;26.7.2.1 Synthesis of Product Subclass 2;1024
1.14.2.1.1;26.7.2.1.1 Method 1: By Alkynylation of Enolates;1024
1.14.2.1.2;26.7.2.1.2 Method 2: By Rearrangement of 3-Furyllithium;1025
1.14.2.1.3;26.7.2.1.3 Method 3: By 1,2-Shift of an Alkynyl Group;1025
1.14.3;26.7.3 Product Subclass 3: .,d-Alkynyl Ketones
;1026
1.14.3.1;26.7.3.1 Synthesis of Product Subclass 3;1027
1.14.3.1.1;26.7.3.1.1 Method 1: By Conjugate Addition to ß,ß-Unsaturated Ketones
;1027
1.14.3.1.1.1;26.7.3.1.1.1 Variation 1: Addition of Alkynylaluminum Reagents;1027
1.14.3.1.1.2;26.7.3.1.1.2 Variation 2: Addition of Alkynylboronates;1027
1.14.3.1.1.3;26.7.3.1.1.3 Variation 3: Transition-Metal-Catalyzed Addition of Terminal Alkynes;1028
1.14.3.1.2;26.7.3.1.2 Method 2: By Propargylation of Enolates;1029
1.14.3.1.3;26.7.3.1.3 Method 3: By Fragmentation;1029
1.14.4;26.7.4 Product Subclass 4: Other Alkynyl Ketones;1030
1.14.4.1;26.7.4.1 Synthesis of Product Subclass 4;1030
1.14.4.1.1;26.7.4.1.1 Method 1: By Eschenmoser Fragmentation;1030
1.15;26.8 Product Class 8: Aryl Ketones;1034
1.15.1;26.8.1 Product Subclass 1: Nonsubstituted and Carbon-Substituted Aryl Ketones;1034
1.15.1.1;26.8.1.1 Synthesis of Product Subclass 1;1034
1.15.1.1.1;26.8.1.1.1 Method 1: Friedel--Crafts Acylation;1034
1.15.1.1.2;26.8.1.1.2 Method 2: Oxidation;1036
1.15.1.1.2.1;26.8.1.1.2.1 Variation 1: Oxidation of Benzylic Halides;1036
1.15.1.1.2.2;26.8.1.1.2.2 Variation 2: Oxidation of Benzylic Alcohols and Ethers;1037
1.15.1.1.2.3;26.8.1.1.2.3 Variation 3: Oxidation of Benzylic Sulfur Compounds;1038
1.15.1.1.2.4;26.8.1.1.2.4 Variation 4: Oxidation of Benzylic Nitrogen Compounds;1039
1.15.1.1.2.5;26.8.1.1.2.5 Variation 5: Oxidative Decyanation;1039
1.15.1.1.2.6;26.8.1.1.2.6 Variation 6: Benzylic Oxidation;1040
1.15.1.1.2.7;26.8.1.1.2.7 Variation 7: Wacker Oxidation;1042
1.15.1.1.3;26.8.1.1.3 Method 3: Acylation of Organometallic Reagents;1042
1.15.1.1.3.1;26.8.1.1.3.1 Variation 1: Arylstannyl Reagents;1043
1.15.1.1.3.2;26.8.1.1.3.2 Variation 2: Arylboryl Reagents;1043
1.15.1.1.3.3;26.8.1.1.3.3 Variation 3: Aryl Grignard Reagents;1044
1.15.1.1.3.4;26.8.1.1.3.4 Variation 4: Aryllithium Reagents;1045
1.15.1.1.3.5;26.8.1.1.3.5 Variation 5: Miscellaneous Aryl Organometallic Reagents;1046
1.15.1.1.4;26.8.1.1.4 Method 4: Transition-Metal-Catalyzed Carbonylation of Aryl Halides and Pseudohalides;1047
1.15.1.1.5;26.8.1.1.5 Method 5: Hydration of Arylalkynes;1048
1.15.1.1.6;26.8.1.1.6 Method 6: Oxidation of Arylalkynes to 1,2-Diketones;1049
1.15.1.1.7;26.8.1.1.7 Method 7: Oxidative Cleavage of gem-Disubstituted Arylalkenes;1049
1.15.1.1.8;26.8.1.1.8 Method 8: Synthesis by Aromatic Ring Formation;1049
1.15.1.1.8.1;26.8.1.1.8.1 Variation 1: Ionic [2 + 2 + 2] Benzannulation;1049
1.15.1.1.8.2;26.8.1.1.8.2 Variation 2: Transition-Metal-Catalyzed [2 + 2 + 2] Benzannulation;1050
1.15.1.1.9;26.8.1.1.9 Method 9: Aryl Ketones by Aromatization of Diels--Alder Adducts;1050
1.15.1.1.10;26.8.1.1.10 Method 10: Aryl Ketones by Electrocyclization and Aromatization;1051
1.15.1.1.11;26.8.1.1.11 Method 11: Transition-Metal-Catalyzed ortho Alkylation of Aryl Ketones;1051
1.15.1.1.12;26.8.1.1.12 Method 12: Transition-Metal-Catalyzed ortho Vinylation of Aryl Ketones;1052
1.15.1.1.13;26.8.1.1.13 Method 13: Transition-Metal-Catalyzed ortho Arylation of Aryl Ketones;1052
1.15.1.2;26.8.1.2 Applications of Product Subclass 1 in Organic Synthesis;1053
1.15.1.2.1;26.8.1.2.1 Method 1: Asymmetric Reduction;1053
1.15.1.2.2;26.8.1.2.2 Method 2: Photochemistry;1053
1.15.1.2.3;26.8.1.2.3 Method 3: Willgerodt Reaction;1054
1.15.1.2.4;26.8.1.2.4 Method 4: 1,2-Aryl Shift;1055
1.15.1.2.5;26.8.1.2.5 Method 5: Haller--Bauer Reaction;1056
1.15.2;26.8.2 Product Subclass 2: Heteroatom-Substituted Aryl Ketones;1057
1.15.2.1;26.8.2.1 Synthesis of Product Subclass 2;1057
1.15.2.1.1;26.8.2.1.1 Method 1: Friedel--Crafts Acylation;1057
1.15.2.1.1.1;26.8.2.1.1.1 Variation 1: Halogen-Substituted Aryl Ketones;1057
1.15.2.1.1.2;26.8.2.1.1.2 Variation 2: Oxygen-Substituted Aryl Ketones;1058
1.15.2.1.1.3;26.8.2.1.1.3 Variation 3: Sulfur-Substituted Aryl Ketones;1059
1.15.2.1.1.4;26.8.2.1.1.4 Variation 4: Nitrogen-Substituted Aryl Ketones;1059
1.15.2.1.2;26.8.2.1.2 Method 2: Houben--Hoesch Reaction;1060
1.15.2.1.3;26.8.2.1.3 Method 3: Fries Rearrangement;1060
1.15.2.1.3.1;26.8.2.1.3.1 Variation 1: Hydroxy-Substituted Aryl Ketones;1060
1.15.2.1.3.2;26.8.2.1.3.2 Variation 2: Amino-Substituted Aryl Ketones;1061
1.15.2.1.4;26.8.2.1.4 Method 4: Hydroxy-Substituted Diaryl Ketones by Acyl Radical ipso Substitution;1062
1.15.2.1.5;26.8.2.1.5 Method 5: Aryl Ring Formation;1062
1.15.2.1.5.1;26.8.2.1.5.1 Variation 1: Amino-Substituted Aryl Ketones by Ionic [2 + 2 + 2] Aromatic Ring Formation;1062
1.15.2.1.5.2;26.8.2.1.5.2 Variation 2: Hydroxy-Substituted Aryl Ketones by [3 + 3] Aromatic Ring Formation;1063
1.15.2.1.5.3;26.8.2.1.5.3 Variation 3: Heteroatom-Substituted Aryl Ketones by [4 + 2] Aromatic Ring Formation: Aromatization of Cycloadducts Derived from Cyanophthalides;1064
1.15.2.1.5.4;26.8.2.1.5.4 Variation 4: Heteroatom-Substituted Aryl Ketones by [4 + 2] Aromatic Ring Formation: Aromatization of Adducts Derived from Activated Cyanomethylene Compounds;1064
1.15.2.1.5.5;26.8.2.1.5.5 Variation 5: Beirut Reaction;1064
1.15.2.1.5.6;26.8.2.1.5.6 Variation 6: Aromatization of Diels--Alder Adducts;1065
1.15.2.1.6;26.8.2.1.6 Method 6: Heteroatom-Substituted Aryl Ketones by Intramolecular Cyclization and Aromatization;1066
1.15.2.1.6.1;26.8.2.1.6.1 Variation 1: Intramolecular Anionic Condensation;1066
1.15.2.1.6.2;26.8.2.1.6.2 Variation 2: Radical Oxidative Cyclization;1066
1.15.2.2;26.8.2.2 Applications of Product Subclass 2 in Organic Synthesis;1067
1.15.2.2.1;26.8.2.2.1 Method 1: Friedländer Quinoline Synthesis;1067
1.15.3;26.8.3 Product Subclass 3: Aryl Ketones with the Carbonyl in a Ring;1068
1.15.3.1;26.8.3.1 Synthesis of Product Subclass 3;1068
1.15.3.1.1;26.8.3.1.1 Method 1: Intramolecular Acylation by Electrophilic Aromatic Substitution;1068
1.15.3.1.2;26.8.3.1.2 Method 2: Intramolecular Alkylation by Electrophilic Aromatic Substitution;1069
1.15.3.1.3;26.8.3.1.3 Method 3: Free Radical Cyclization onto Aromatic Rings;1071
1.15.3.1.4;26.8.3.1.4 Method 4: Intramolecular Alkylation of Aromatic Carboxylic Acid Derivatives;1072
1.15.3.1.5;26.8.3.1.5 Method 5: Cyclization of Aroyl Radicals;1072
1.15.3.1.6;26.8.3.1.6 Method 6: Benzocyclobutanones from Heteroatom-Substituted Benzoyl Compounds;1073
1.15.3.1.7;26.8.3.1.7 Method 7: [2 + 2] Cycloaddition to Benzyne Species Generated from Aromatic Halides;1073
1.15.3.1.8;26.8.3.1.8 Method 8: Acylation and Carbonylation of Aryl Metallic Species Generated from Aromatic Halides;1075
1.15.3.1.9;26.8.3.1.9 Method 9: By Ring Formation;1076
1.15.3.1.9.1;26.8.3.1.9.1 Variation 1: By Transition-Metal-Catalyzed [2 + 2 + 2] Aromatic Ring Formation;1076
1.15.3.1.9.2;26.8.3.1.9.2 Variation 2: By [3 + 3] Aromatic Ring Formation;1076
1.15.3.1.9.3;26.8.3.1.9.3 Variation 3: By [4 + 2] Aromatic Ring Formation;1076
1.15.3.1.9.4;26.8.3.1.9.4 Variation 4: By Electrocyclization and Aromatization;1078
1.16;26.9 Product Class 9: Enones;1090
1.16.1;26.9.1 Product Subclass 1: a,ß-Unsaturated Ketones
;1090
1.16.1.1;26.9.1.1 Synthesis of Product Subclass 1;1090
1.16.1.1.1;26.9.1.1.1 Method 1: Oxidation Adjacent to Alkenes;1090
1.16.1.1.1.1;26.9.1.1.1.1 Variation 1: Allylic Oxidation with Stoichiometric Chromium Reagents;1090
1.16.1.1.1.2;26.9.1.1.1.2 Variation 2: Allylic Oxidation with Peroxides and Catalytic Metal Salts;1091
1.16.1.1.1.3;26.9.1.1.1.3 Variation 3: Allylic Oxidation with Selenium Reagents;1092
1.16.1.1.2;26.9.1.1.2 Method 2: Oxidation of Allylic Alcohols;1093
1.16.1.1.3;26.9.1.1.3 Method 3: Acylation of Organometallic Reagents;1095
1.16.1.1.3.1;26.9.1.1.3.1 Variation 1: Addition of Alkenylmetals to Carboxylic Acids;1095
1.16.1.1.3.2;26.9.1.1.3.2 Variation 2: Addition of Alkenylmetals to Carboxylic Esters and Derivatives;1096
1.16.1.1.3.3;26.9.1.1.3.3 Variation 3: Addition of Alkenylmetals to Carboxylic Amides and Derivatives;1097
1.16.1.1.3.4;26.9.1.1.3.4 Variation 4: Direct Addition of Alkenylmetals to Carboxylic Acid Halides and Anhydrides;1098
1.16.1.1.3.5;26.9.1.1.3.5 Variation 5: Lewis Acid Catalyzed Addition of Alkenylmetals to Carboxylic Acid Halides and Anhydrides;1100
1.16.1.1.3.6;26.9.1.1.3.6 Variation 6: Transition-Metal-Catalyzed Coupling of Alkenylmetals with Carboxylic Acid Halides and Anhydrides;1101
1.16.1.1.3.7;26.9.1.1.3.7 Variation 7: Transition-Metal-Catalyzed Coupling of Alkenylmetals with Organic Halides and Carbon Monoxide;1102
1.16.1.1.3.8;26.9.1.1.3.8 Variation 8: Addition of Alkenylmetals to Nitriles;1103
1.16.1.1.3.9;26.9.1.1.3.9 Variation 9: Addition of Organometallics to a,ß-Unsaturated Carboxylic Acids
;1104
1.16.1.1.3.10;26.9.1.1.3.10 Variation 10: Addition of Organometallics to a,ß-Unsaturated Carboxylic Amides
;1104
1.16.1.1.3.11;26.9.1.1.3.11 Variation 11: Transition-Metal-Catalyzed Coupling of Organometallics with Alkenyl Acid Halides;1105
1.16.1.1.3.12;26.9.1.1.3.12 Variation 12: Transition-Metal-Mediated Coupling of Organometallics with Alkenyl Halides and Carbon Monoxide;1107
1.16.1.1.3.13;26.9.1.1.3.13 Variation 13: Addition of Organometallics to a,ß-Unsaturated Nitriles
;1108
1.16.1.1.4;26.9.1.1.4 Method 4: Substitution of Alkenes;1108
1.16.1.1.4.1;26.9.1.1.4.1 Variation 1: Lewis Acid Catalyzed Substitution with Acid Halides;1108
1.16.1.1.4.2;26.9.1.1.4.2 Variation 2: Transition-Metal-Catalyzed Substitution with Acid Halides;1109
1.16.1.1.5;26.9.1.1.5 Method 5: Elimination Reactions;1110
1.16.1.1.5.1;26.9.1.1.5.1 Variation 1: Oxidative Elimination of Metal Hydride from Enol Derivatives;1110
1.16.1.1.5.2;26.9.1.1.5.2 Variation 2: Elimination of a Hydrogen Halide from a-Halo Ketones
;1111
1.16.1.1.5.3;26.9.1.1.5.3 Variation 3: Elimination from ß-Heterosubstituted Ketones
;1112
1.16.1.1.5.4;26.9.1.1.5.4 Variation 4: Pericyclic Elimination of a-Sulfinyl and a-Seleninyl Ketones
;1114
1.16.1.1.5.5;26.9.1.1.5.5 Variation 5: Pericyclic Elimination of ß-Acetoxy, ß-Sulfinyl, and ß-Seleninyl Ketones
;1115
1.16.1.1.6;26.9.1.1.6 Method 6: Reduction of Propargylic Ketones;1116
1.16.1.1.7;26.9.1.1.7 Method 7: Organometallic Addition to ß-Heterosubstituted a,ß-Unsaturated Ketones
;1117
1.16.1.1.7.1;26.9.1.1.7.1 Variation 1: Direct Substitution;1117
1.16.1.1.7.2;26.9.1.1.7.2 Variation 2: Substitution by Addition/Rearrangement;1118
1.16.1.1.8;26.9.1.1.8 Method 8: Aldol Condensation;1119
1.16.1.1.8.1;26.9.1.1.8.1 Variation 1: Intermolecular Aldol Reaction of Ketones;1119
1.16.1.1.8.2;26.9.1.1.8.2 Variation 2: Intermolecular Aldol Reaction of Enamines and Enol Ethers;1120
1.16.1.1.8.3;26.9.1.1.8.3 Variation 3: Intramolecular Aldol Condensation;1122
1.16.1.1.8.4;26.9.1.1.8.4 Variation 4: Tandem Michael Addition/Intramolecular Aldol Reaction (Robinson Annulation);1123
1.16.1.1.9;26.9.1.1.9 Method 9: Wittig-Type Alkenations;1125
1.16.1.1.9.1;26.9.1.1.9.1 Variation 1: Wittig Reaction of Oxophosphoranes;1125
1.16.1.1.9.2;26.9.1.1.9.2 Variation 2: Horner--Wittig Reaction of Oxophosphine Oxides;1127
1.16.1.1.9.3;26.9.1.1.9.3 Variation 3: Horner--Wadsworth--Emmons Reaction;1127
1.16.1.1.9.4;26.9.1.1.9.4 Variation 4: Peterson Reaction of a-Silyl Ketones
;1129
1.16.1.1.9.5;26.9.1.1.9.5 Variation 5: Wittig Alkenation of 1,2-Dicarbonyls;1130
1.16.1.1.10;26.9.1.1.10 Method 10: Cyclocondensation of Danishefsky-Type Dienes with Alkenes;1131
1.16.1.1.11;26.9.1.1.11 Method 11: Union of Alkynes, Alkenes, and Carbon Monoxide;1132
1.16.1.1.11.1;26.9.1.1.11.1 Variation 1: Using Hexacarbonyldicobalt--Alkyne Complexes (Pauson--Khand Reaction);1132
1.16.1.1.11.2;26.9.1.1.11.2 Variation 2: By Direct Transition-Metal-Promoted Coupling;1134
1.16.1.1.12;26.9.1.1.12 Method 12: Transition-Metal-Catalyzed Addition of Aryl Halides and Carbon Monoxide to Allenes;1135
1.16.1.1.13;26.9.1.1.13 Method 13: Addition of Nucleophiles to Propargylic Ketones;1136
1.16.1.1.14;26.9.1.1.14 Method 14: a-Alkylation of Preformed a,ß-Unsaturated Ketones
;1138
1.16.1.1.14.1;26.9.1.1.14.1 Variation 1: By Base-Mediated Dienolate Formation;1138
1.16.1.1.14.2;26.9.1.1.14.2 Variation 2: By Catalyzed Nucleophilic Addition/Alkylation/Elimination;1139
1.16.1.1.15;26.9.1.1.15 Method 15: a'-Alkylation of Preformed a,ß-Unsaturated Ketones
;1140
1.16.1.1.16;26.9.1.1.16 Method 16: .-Alkylation of Preformed a,ß-Unsaturated Enones
;1141
1.16.1.1.16.1;26.9.1.1.16.1 Variation 1: By Direct .-Alkylation
;1141
1.16.1.1.16.2;26.9.1.1.16.2 Variation 2: By a'-Alkylation of Vinylogous Esters with Rearrangement
;1142
1.16.1.1.17;26.9.1.1.17 Method 17: Alkylation of Umpoled Enal Anion Equivalents;1143
1.16.1.1.18;26.9.1.1.18 Method 18: Hydroacylation of Alkynes;1144
1.16.1.1.19;26.9.1.1.19 Method 19: Oxidative Ring Opening of Furans;1145
1.16.1.1.20;26.9.1.1.20 Method 20: Retro-Diels--Alder Reaction;1146
1.16.1.1.21;26.9.1.1.21 Method 21: Nazarov Cyclization of Dienones;1147
1.16.1.1.22;26.9.1.1.22 Method 22: Isomerization of Propargylic Alcohols;1148
1.16.1.1.23;26.9.1.1.23 Method 23: Alkene Metathesis;1149
1.16.2;26.9.2 Product Subclass 2: ß,.-Unsaturated Ketones
;1150
1.16.2.1;26.9.2.1 Synthesis of Product Subclass 2;1150
1.16.2.1.1;26.9.2.1.1 Method 1: Acylation of Allyl Organometallics;1150
1.16.2.1.1.1;26.9.2.1.1.1 Variation 1: Addition of Allylmetals to Carboxylic Acids;1151
1.16.2.1.1.2;26.9.2.1.1.2 Variation 2: Addition of Allylmetals to Carboxylic Amides;1151
1.16.2.1.1.3;26.9.2.1.1.3 Variation 3: Addition of Allylmetals to Reactive Carboxylic Acid Derivatives;1152
1.16.2.1.1.4;26.9.2.1.1.4 Variation 4: Addition of Allylmetals to Nitriles;1154
1.16.2.1.2;26.9.2.1.2 Method 2: Deconjugative Alkylation of a,ß-Unsaturated Ketones
;1154
1.16.2.1.3;26.9.2.1.3 Method 3: Transition-Metal-Catalyzed Vinylation of Enolates;1155
1.16.3;26.9.3 Product Subclass 3: .,d-Unsaturated Ketones
;1156
1.16.3.1;26.9.3.1 Synthesis of Product Subclass 3;1156
1.16.3.1.1;26.9.3.1.1 Method 1: Coupling of Enolates with Transition-Metal--Allyl Complexes;1156
1.16.3.1.2;26.9.3.1.2 Method 2: Claisen Rearrangement;1160
1.16.4;26.9.4 Product Subclass 4: d,e-Unsaturated Ketones
;1160
1.17;26.10 Product Class 10: Saturated and Unsaturated Ketones with an Additional Carbonyl, Nitrile, or Carboxy Substituent or Equivalent at a ß- or More Remote Position: Synthesis of the Ketone Functionality
;1168
1.18;26.10 Product Class 10: Saturated and Unsaturated Ketones with anAdditional Carbonyl, Nitrile, or Carboxy Substituent or Equivalent at a ß- or More Remote Position: Synthesis of the Ketone Functionality
;1168
1.18.1;26.10.1 Product Subclass 1: Oxonitriles;1168
1.18.1.1;26.10.1.1 Synthesis of Product Subclass 1;1169
1.18.1.1.1;26.10.1.1.1 Method 1: Oxidation;1169
1.18.1.1.1.1;26.10.1.1.1.1 Variation 1: Of Hydroxynitriles;1169
1.18.1.1.1.2;26.10.1.1.1.2 Variation 2: Of Nitronitriles;1169
1.18.1.1.1.3;26.10.1.1.1.3 Variation 3: Of Unsaturated Nitriles;1170
1.18.1.1.2;26.10.1.1.2 Method 2: Electrophilic Acylation of Nitriles;1171
1.18.1.1.2.1;26.10.1.1.2.1 Variation 1: With Acyl Halides;1171
1.18.1.1.2.2;26.10.1.1.2.2 Variation 2: With Carboxylic Acids, Esters, or Anhydrides;1172
1.18.1.1.2.3;26.10.1.1.2.3 Variation 3: With Amides and Nitriles;1173
1.18.1.1.3;26.10.1.1.3 Method 3: Nucleophilic Acylation of Cyano Derivatives;1174
1.18.1.1.3.1;26.10.1.1.3.1 Variation 1: With Aldehydes and Derivatives (Cyanohydrins);1174
1.18.1.1.3.2;26.10.1.1.3.2 Variation 2: With Metal--Carbonyl Complexes;1175
1.18.1.1.3.3;26.10.1.1.3.3 Variation 3: With Miscellaneous Nucleophiles;1176
1.18.1.1.4;26.10.1.1.4 Method 4: Radical Acylation of Cyano Derivatives;1176
1.18.1.1.4.1;26.10.1.1.4.1 Variation 1: With Anhydrides or Aldehydes;1177
1.18.1.1.4.2;26.10.1.1.4.2 Variation 2: With Selenoesters;1177
1.18.1.1.4.3;26.10.1.1.4.3 Variation 3: With Transition-Metal Complexes;1178
1.18.1.1.4.4;26.10.1.1.4.4 Variation 4: With ß-Acyl Radicals
;1179
1.18.1.1.5;26.10.1.1.5 Method 5: Carbonylation of Cyano Compounds;1179
1.18.1.1.5.1;26.10.1.1.5.1 Variation 1: Free-Radical Carbonylation Reactions;1179
1.18.1.1.5.2;26.10.1.1.5.2 Variation 2: With Transition-Metal Complexes;1181
1.18.1.1.6;26.10.1.1.6 Method 6: Ring-Opening and Ring-Expansion Reactions;1181
1.18.1.1.7;26.10.1.1.7 Method 7: Cyclizations and Cycloadditions;1183
1.18.1.1.7.1;26.10.1.1.7.1 Variation 1: Thorpe--Ziegler and Related Cyclizations;1183
1.18.1.1.7.2;26.10.1.1.7.2 Variation 2: Cycloaddition Reactions;1184
1.18.1.1.7.3;26.10.1.1.7.3 Variation 3: Other Concerted Reactions;1185
1.18.1.1.8;26.10.1.1.8 Method 8: Hydrolysis;1186
1.18.1.1.9;26.10.1.1.9 Methods 9: Miscellaneous Methods;1187
1.18.2;26.10.2 Product Subclass 2: Oxo Esters and Oxo Amides;1187
1.18.2.1;26.10.2.1 Synthesis of Product Subclass 2;1188
1.18.2.1.1;26.10.2.1.1 Method 1: Oxidation;1188
1.18.2.1.1.1;26.10.2.1.1.1 Variation 1: From Oxygen-Containing Carbonyl Compounds;1188
1.18.2.1.1.2;26.10.2.1.1.2 Variation 2: From Nitrogen-Containing Carbonyl Compounds;1190
1.18.2.1.1.3;26.10.2.1.1.3 Variation 3: From Unsaturated Carbonyl Compounds;1191
1.18.2.1.2;26.10.2.1.2 Method 2: Electrophilic Acylation;1194
1.18.2.1.2.1;26.10.2.1.2.1 Variation 1: With Acyl Halides and Acyl Cyanides;1194
1.18.2.1.2.2;26.10.2.1.2.2 Variation 2: With Carboxylic Acids, Anhydrides, or Esters;1196
1.18.2.1.2.3;26.10.2.1.2.3 Variation 3: With Amides or Nitriles;1198
1.18.2.1.2.4;26.10.2.1.2.4 Variation 4: With Miscellaneous Electrophiles;1200
1.18.2.1.3;26.10.2.1.3 Method 3: Nucleophilic Acylation;1201
1.18.2.1.3.1;26.10.2.1.3.1 Variation 1: With Aldehydes (via Cyanohydrins and Related Compounds);1201
1.18.2.1.3.2;26.10.2.1.3.2 Variation 2: With Metal--Carbonyl Reagents;1202
1.18.2.1.3.3;26.10.2.1.3.3 Variation 3: With Miscellaneous Nucleophiles;1203
1.18.2.1.4;26.10.2.1.4 Method 4: Radical Acylation of Unsaturated Carbonyl Compounds;1205
1.18.2.1.4.1;26.10.2.1.4.1 Variation 1: With Aldehydes;1205
1.18.2.1.4.2;26.10.2.1.4.2 Variation 2: With Anhydrides;1206
1.18.2.1.4.3;26.10.2.1.4.3 Variation 3: With Selenoesters;1207
1.18.2.1.4.4;26.10.2.1.4.4 Variation 4: With Cyclopropanols;1209
1.18.2.1.5;26.10.2.1.5 Method 5: Carbonylation;1209
1.18.2.1.5.1;26.10.2.1.5.1 Variation 1: The Pauson--Khand Reaction;1210
1.18.2.1.5.2;26.10.2.1.5.2 Variation 2: Free-Radical Carbonylation;1212
1.18.2.1.5.3;26.10.2.1.5.3 Variation 3: With Organometallic Complexes;1214
1.18.2.1.6;26.10.2.1.6 Method 6: By Rearrangement;1215
1.18.2.1.6.1;26.10.2.1.6.1 Variation 1: Ring Expansions by Radical Methods;1215
1.18.2.1.6.2;26.10.2.1.6.2 Variation 2: Ring Expansion by Nonradical Methods;1217
1.18.2.1.6.3;26.10.2.1.6.3 Variation 3: Electrocyclic Rearrangements;1219
1.18.2.1.6.4;26.10.2.1.6.4 Variation 4: Miscellaneous Rearrangements;1221
1.18.2.1.7;26.10.2.1.7 Method 7: Cyclization and Cycloaddition;1223
1.18.2.1.7.1;26.10.2.1.7.1 Variation 1: Dieckmann Condensation;1223
1.18.2.1.7.2;26.10.2.1.7.2 Variation 2: Cycloadditions and Miscellaneous Cyclizations;1225
1.18.2.1.8;26.10.2.1.8 Methods 8: Miscellaneous Methods;1227
1.18.2.1.8.1;26.10.2.1.8.1 Variation 1: Solvolyses;1227
1.18.2.1.8.2;26.10.2.1.8.2 Variation 2: Hydration of Alkynes;1229
1.18.2.1.8.3;26.10.2.1.8.3 Variation 3: Arylation of Baylis--Hillman Adducts;1229
1.18.3;26.10.3 Product Subclass 3: Diketones and Oxo Imines;1230
1.18.3.1;26.10.3.1 Synthesis of Product Subclass 3;1231
1.18.3.1.1;26.10.3.1.1 Method 1: Oxidation;1231
1.18.3.1.1.1;26.10.3.1.1.1 Variation 1: Of Hydroxy Ketones and Diols;1231
1.18.3.1.1.2;26.10.3.1.1.2 Variation 2: Of Nitro Ketones;1233
1.18.3.1.1.3;26.10.3.1.1.3 Variation 3: Of Alkanones and Alkenones;1234
1.18.3.1.1.4;26.10.3.1.1.4 Variation 4: Of Sulfur-Containing Compounds;1235
1.18.3.1.2;26.10.3.1.2 Method 2: Electrophilic Acylation;1236
1.18.3.1.2.1;26.10.3.1.2.1 Variation 1: With Acyl Halides and Acyl Cyanides;1236
1.18.3.1.2.2;26.10.3.1.2.2 Variation 2: With Anhydrides, Carboxylic Acids, and Esters;1238
1.18.3.1.2.3;26.10.3.1.2.3 Variation 3: Of Amides;1240
1.18.3.1.3;26.10.3.1.3 Method 3: Nucleophilic Acylation;1240
1.18.3.1.3.1;26.10.3.1.3.1 Variation 1: By Aldehydes (via Cyanohydrins and Related Compounds);1240
1.18.3.1.3.2;26.10.3.1.3.2 Variation 2: By Metal--Carbonyl Reagents;1241
1.18.3.1.4;26.10.3.1.4 Method 4: By Radical Acylation of a,ß-Unsaturated Ketones
;1243
1.18.3.1.4.1;26.10.3.1.4.1 Variation 1: By Acyl Radicals;1243
1.18.3.1.4.2;26.10.3.1.4.2 Variation 2: By Carbon Monoxide Gas;1244
1.18.3.1.5;26.10.3.1.5 Method 5: Carbonylation of Functionalized Ketones;1245
1.18.3.1.5.1;26.10.3.1.5.1 Variation 1: By the Pauson--Khand Reaction;1245
1.18.3.1.5.2;26.10.3.1.5.2 Variation 2: With Organorhodium and Organopalladium Compounds;1246
1.18.3.1.6;26.10.3.1.6 Method 6: Rearrangement;1247
1.18.3.1.6.1;26.10.3.1.6.1 Variation 1: Ring Opening of Oxygenated Heterocycles;1247
1.18.3.1.6.2;26.10.3.1.6.2 Variation 2: Ring Opening of Cycloalkanes;1248
1.18.3.1.6.3;26.10.3.1.6.3 Variation 3: Ring Expansion;1250
1.18.3.1.6.4;26.10.3.1.6.4 Variation 4: Sigmatropic Rearrangement;1250
1.18.3.1.7;26.10.3.1.7 Method 7: Hydration/Hydrolysis;1251
1.18.3.1.7.1;26.10.3.1.7.1 Variation 1: From Alkynones;1251
1.18.3.1.7.2;26.10.3.1.7.2 Variation 2: From Ene Halides;1252
1.18.3.1.7.3;26.10.3.1.7.3 Variation 3: From Nonoxygenated Acetals or Other Functions;1253
1.19;26.11 Product Class 11: Saturated and Unsaturated Ketones with a ß- or More Remote Heteroatom Substituent
;1270
1.19.1;26.11.1 Product Subclass 1: Halo Ketones;1270
1.19.1.1;26.11.1.1 Synthesis of Product Subclass 1;1270
1.19.1.1.1;26.11.1.1.1 Method 1: Oxidation of Halo Alcohols;1270
1.19.1.1.2;26.11.1.1.2 Method 2: Electrophilic Acylation of Acid Chlorides and Anhydrides;1271
1.19.1.1.3;26.11.1.1.3 Method 3: Nucleophilic Acylation of a-Chloro Ketones
;1272
1.19.1.1.4;26.11.1.1.4 Method 4: Carbonylation of Aliphatic Dihalides;1272
1.19.1.1.5;26.11.1.1.5 Method 5: Rearrangement;1273
1.19.1.1.5.1;26.11.1.1.5.1 Variation 1: Ring Opening of Cyclopropyl Silyl Ethers;1273
1.19.1.1.5.2;26.11.1.1.5.2 Variation 2: Decomposition of Tertiary Alkyl Hypochlorites;1273
1.19.1.1.6;26.11.1.1.6 Method 6: Hydrolysis of Hydrazones;1274
1.19.1.1.7;26.11.1.1.7 Methods 7: Miscellaneous Reactions;1274
1.19.2;26.11.2 Product Subclass 2: Hydroxy and Sulfanyl Ketones and Derivatives;1275
1.19.2.1;26.11.2.1 Synthesis of Product Subclass 2;1275
1.19.2.1.1;26.11.2.1.1 Method 1: Oxidation;1275
1.19.2.1.1.1;26.11.2.1.1.1 Variation 1: From Monoprotected Diols and Hydroxy Sulfides;1275
1.19.2.1.1.2;26.11.2.1.1.2 Variation 2: From Unprotected Diols;1277
1.19.2.1.1.3;26.11.2.1.1.3 Variation 3: From Nitro Compounds;1278
1.19.2.1.1.4;26.11.2.1.1.4 Variation 4: From Alkanes and Alkenes;1279
1.19.2.1.2;26.11.2.1.2 Method 2: Electrophilic Acylation;1281
1.19.2.1.2.1;26.11.2.1.2.1 Variation 1: From Acyl Halides;1281
1.19.2.1.2.2;26.11.2.1.2.2 Variation 2: From Hydroxy- and Sulfanyl-Substituted Carboxylic Acids, Esters, and Thioesters;1282
1.19.2.1.2.3;26.11.2.1.2.3 Variation 3: From Hydroxy- and Sulfur-Substituted Amides and Nitriles;1284
1.19.2.1.3;26.11.2.1.3 Method 3: Hetero-Michael Additions;1285
1.19.2.1.3.1;26.11.2.1.3.1 Variation 1: Addition of Alcohols;1285
1.19.2.1.3.2;26.11.2.1.3.2 Variation 2: Addition of Thiols;1286
1.19.2.1.4;26.11.2.1.4 Method 4: Nucleophilic Acylation;1287
1.19.2.1.4.1;26.11.2.1.4.1 Variation 1: From Cyanohydrins;1287
1.19.2.1.4.2;26.11.2.1.4.2 Variation 2: From Isocyanides;1288
1.19.2.1.4.3;26.11.2.1.4.3 Variation 3: From a-Sulfanyl Sulfones
;1288
1.19.2.1.5;26.11.2.1.5 Method 5: Radical Acylation;1289
1.19.2.1.6;26.11.2.1.6 Method 6: Carbonylation;1290
1.19.2.1.7;26.11.2.1.7 Method 7: Rearrangement;1292
1.19.2.1.7.1;26.11.2.1.7.1 Variation 1: Ferrier and Petasis Rearrangement;1292
1.19.2.1.7.2;26.11.2.1.7.2 Variation 2: Pinacol and Related Rearrangements;1293
1.19.2.1.7.3;26.11.2.1.7.3 Variation 3: Ring Opening;1294
1.19.2.1.7.4;26.11.2.1.7.4 Variation 4: Ring Expansion;1295
1.19.2.1.7.5;26.11.2.1.7.5 Variation 5: Electrocyclic Rearrangements;1296
1.19.2.1.8;26.11.2.1.8 Method 8: Cyclization and Cycloaddition;1297
1.19.2.1.9;26.11.2.1.9 Method 9: Hydrolysis and Hydration Reactions;1298
1.19.2.1.10;26.11.2.1.10 Methods 10: Miscellaneous Reactions;1299
1.19.3;26.11.3 Product Subclass 3: Amino and Phosphono Ketones and Derivatives;1299
1.19.3.1;26.11.3.1 Synthesis of Product Subclass 3;1300
1.19.3.1.1;26.11.3.1.1 Method 1: Oxidation;1300
1.19.3.1.1.1;26.11.3.1.1.1 Variation 1: From Amino Alcohol Derivatives;1300
1.19.3.1.1.2;26.11.3.1.1.2 Variation 2: From Amino Nitrogenated and Related Compounds;1300
1.19.3.1.1.3;26.11.3.1.1.3 Variation 3: From Alkyl-, Alkenyl-, and Alkynylamines;1301
1.19.3.1.2;26.11.3.1.2 Method 2: Electrophilic Acylations;1303
1.19.3.1.2.1;26.11.3.1.2.1 Variation 1: From Acyl Halides;1303
1.19.3.1.2.2;26.11.3.1.2.2 Variation 2: From Carboxylic Acids, Esters, Lactones, and Anhydrides;1305
1.19.3.1.2.3;26.11.3.1.2.3 Variation 3: From Amino Amides, Lactams, and Aminonitriles;1306
1.19.3.1.2.4;26.11.3.1.2.4 Variation 4: Conjugate Additions to a,ß-Unsaturated Ketones
;1308
1.19.3.1.3;26.11.3.1.3 Method 3: By Carbonylation;1309
1.19.3.1.3.1;26.11.3.1.3.1 Variation 1: Via the Pauson--Khand Reaction;1309
1.19.3.1.3.2;26.11.3.1.3.2 Variation 2: By Other Carbonylative Methods;1311
1.19.3.1.4;26.11.3.1.4 Method 4: By Rearrangements, Cycloadditions, and Cyclizations;1312
1.19.3.1.4.1;26.11.3.1.4.1 Variation 1: Pinacol-Type Rearrangements;1312
1.19.3.1.4.2;26.11.3.1.4.2 Variation 2: Ring Openings;1312
1.19.3.1.4.3;26.11.3.1.4.3 Variation 3: Ring Expansions;1313
1.19.3.1.4.4;26.11.3.1.4.4 Variation 4: Electrocyclic Rearrangements;1315
1.19.3.1.4.5;26.11.3.1.4.5 Variation 5: Cycloadditions and Cyclizations;1315
1.19.3.1.4.6;26.11.3.1.4.6 Variation 6: Miscellaneous Rearrangements;1317
1.19.3.1.5;26.11.3.1.5 Method 5: By Hydration/Hydrolysis;1318
1.19.3.1.5.1;26.11.3.1.5.1 Variation 1: Hydrolysis;1318
1.19.3.1.5.2;26.11.3.1.5.2 Variation 2: Hydrations;1319
1.20;Keyword Index;1332
1.21;Author Index;1386
1.22;Abbreviations;1462mehr

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