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Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 20b

Three Carbon-Heteroatom Bonds: Esters, and Lactones; Peroxy Acids and R(CO)OX Compounds; R(CO)X, X=S, Se, Te

Autor	Daniel Bellus, Gwilherm Evano, Julien Beignet, Robert Garbacci, Sherry R. Chemler, Steven J. Collier
Verlag	Georg Thieme Verlag KG
Erscheinungsjahr	2014
Seitenanzahl	1165 Seiten
ISBN	9783131719416
Format	PDF/ePUB
Kopierschutz	Wasserzeichen
Geräte	PC/MAC/eReader/Tablet
Preis	2199,99 EUR

Science of Synthesis provides a critical review of the synthetic methodology developed from the early 1800s to date for the entire field of organic and organometallic chemistry. As the only resource providing full-text descriptions of organic transformations and synthetic methods as well as experimental procedures, Science of Synthesis is therefore a unique chemical information tool. Over 1000 world-renowned experts have chosen the most important molecular transformations for a class of organic compounds and elaborated on their scope and limitations. The systematic, logical and consistent organization of the synthetic methods for each functional group enables users to quickly find out which methods are useful for a particular synthesis and which are not. Effective and practical experimental procedures can be implemented quickly and easily in the lab.// The content of this e-book was originally published in October 2006.

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Science of Synthesis – Volume 20b: Three Carbon--Heteroatom Bonds: Esters and Lactones	Peroxy Acids and R(CO)OX Compounds	R(CO)X, X = S, Se, Te	1
Title page	3
Imprint	5
Preface	6
Volume Editor's Preface	8
Overview	10
Table of Contents	12
20.5 Product Class 5: Carboxylic Acid Esters	40
20.5.1 Product Subclass 1: Alkyl Alkanoates	40
20.5.1.1 Synthesis from Carbonic Acid Derivatives	62
20.5.1.1.1 Method 1: Use of Carbonic Acid Diesters	62
20.5.1.1.1.1 Variation 1: Reactions with Enolates	62
20.5.1.1.1.2 Variation 2: Reactions with Carbanions without Stabilizing Electron-Withdrawing a-Heteroatom Groups	67
20.5.1.1.1.3 Variation 3: Reaction with a-Heteroatom-Stabilized Carbanions	70
20.5.1.1.1.4 Variation 4: Intramolecular Rearrangements	72
20.5.1.1.2 Method 2: Use of Haloformates	75
20.5.1.1.2.1 Variation 1: Reactions with Enolates	76
20.5.1.1.2.2 Variation 2: Reaction with Carbanions without Stabilizing Electron-Withdrawing a-Heteroatom Groups	80
20.5.1.1.2.3 Variation 3: Reaction with a-Heteroatom-Stabilized Carbanions	85
20.5.1.1.2.4 Variation 4: Other Syntheses	88
20.5.1.1.3 Method 3: Use of Cyanoformate Esters	90
20.5.1.1.3.1 Variation 1: Reaction with Enolates	91
20.5.1.1.3.2 Variation 2: Using Other Carbon Nucleophiles	95
20.5.1.1.3.3 Variation 3: Novel Reactions	97
20.5.1.1.4 Method 4: Use of Di-tert-butyl Dicarbonate	99
20.5.1.2 Synthesis from Carboxylic Acids and Derivatives	108
20.5.1.2.1 Method 1: Synthesis from Carboxylic Acids	108
20.5.1.2.1.1 Variation 1: Phosphorus Activation of Alcohols (Mitsunobu Reaction)	108
20.5.1.2.1.2 Variation 2: Dicyclohexylcarbodiimide Activation of Acids	109
20.5.1.2.1.3 Variation 3: Direct Condensation of Acids and Alcohols Catalyzed by a Lewis Acid	110
20.5.1.2.1.4 Variation 4: Direct Condensation of Acids and Alcohols Using Ammonium Salts	111
20.5.1.2.2 Method 2: Synthesis from Acid Halides	112
20.5.1.2.3 Method 3: Synthesis from Acid Anhydrides	112
20.5.1.2.4 Method 4: Synthesis from Amides	114
20.5.1.2.5 Method 5: Synthesis from 2-Alkyl-4,5-dihydrooxazoles	114
20.5.1.2.6 Method 6: Synthesis from Nitriles	115
20.5.1.2.7 Method 7: Synthesis from Ketenes	116
20.5.1.2.7.1 Variation 1: Nucleophilic Addition of Alcohols	116
20.5.1.2.7.2 Variation 2: Asymmetric Chlorination	119
20.5.1.3 Synthesis from Aldehydes, Ketones, and Derivatives (Including Enol Ethers)	122
20.5.1.3.1 Synthesis from Aldehydes	122
20.5.1.3.1.1 Oxidative Processes	122
20.5.1.3.1.1.1 Method 1: Using Manganese(IV) Oxide and Sodium Cyanide	122
20.5.1.3.1.1.2 Method 2: Using Bromine	124
20.5.1.3.1.1.2.1 Variation 1: Using Pyridinium Tribromide	126
20.5.1.3.1.1.3 Method 3: Using Iodine	127
20.5.1.3.1.1.4 Method 4: Using Pyridinium Dichromate	128
20.5.1.3.1.1.5 Method 5: Using Sodium or Calcium Hypochlorites	129
20.5.1.3.1.1.6 Method 6: Using N-Bromosuccinimide	131
20.5.1.3.1.1.6.1 Variation 1: Using N-Bromosuccinimide and Alkoxytrimethylsilanes or Alkoxytrialkylstannanes	131
20.5.1.3.1.1.7 Method 7: Using N-Iodosuccinimide	132
20.5.1.3.1.1.8 Method 8: Using Caro's Acid	133
20.5.1.3.1.1.9 Method 9: Using Oxone	133
20.5.1.3.1.1.10 Method 10: Using Trichloroisocyanuric Acid	134
20.5.1.3.1.1.11 Method 11: Using Transition-Metal Catalysts	135
20.5.1.3.1.1.12 Method 12: Using Electrochemical Oxidation	136
20.5.1.3.1.1.13 Method 13: Using Ozone	138
20.5.1.3.1.1.14 Method 14: Using Hydrogen Peroxide	139
20.5.1.3.1.2 Oxidation/Reduction Processes	140
20.5.1.3.1.2.1 Method 1: Using the Tishchenko Reaction	140
20.5.1.3.1.2.1.1 Variation 1: Using the Homo Aldol--Tishchenko Reaction	142
20.5.1.3.1.2.1.2 Variation 2: Using the Hetero Aldol--Tishchenko Reaction	142
20.5.1.3.1.2.1.3 Variation 3: Using the Evans--Tishchenko Reaction	144
20.5.1.3.1.2.2 Method 2: Intramolecular Hydroacylation Reactions	146
20.5.1.3.2 Synthesis from Ketones via the Baeyer--Villiger Reaction	147
20.5.1.3.2.1 Method 1: Using Pertrifluoroacetic Acid	148
20.5.1.3.2.2 Method 2: Using Peroxybenzoic Acids	149
20.5.1.3.2.3 Method 3: Using Hydrogen Peroxide	150
20.5.1.3.2.4 Method 4: Using Bis(trimethylsilyl) Peroxide	151
20.5.1.3.2.5 Method 5: Using Enzymes	152
20.5.1.3.3 Synthesis from Acetals	152
20.5.1.3.3.1 Method 1: Using Ozone	152
20.5.1.3.3.2 Method 2: Using Hypochlorous Acid	154
20.5.1.3.3.3 Method 3: Using N-Bromosuccinimide	155
20.5.1.3.3.4 Method 4: Using Peroxy Acids	156
20.5.1.3.3.5 Method 5: Using Oxone	157
20.5.1.3.3.6 Method 6: Using Caro's Acid	158
20.5.1.3.3.7 Method 7: Using tert-Butyl Hydroperoxide and a Catalyst	159
20.5.1.3.3.8 Method 8: Photochemical Oxidation	160
20.5.1.3.3.9 Method 9: Using Potassium Permanganate	160
20.5.1.3.4 Synthesis from Enol Ethers	161
20.5.1.3.4.1 Method 1: Using Ozone	161
20.5.1.3.4.2 Method 2: Using 3-Chloroperoxybenzoic Acid	162
20.5.1.3.4.3 Method 3: Using Chromium(VI) Oxide	163
20.5.1.3.4.4 Method 4: Using Pyridinium Chlorochromate	164
20.5.1.3.5 Synthesis from a-Hydroxy Carbonyl Compounds and 1,2-Diones	165
20.5.1.3.5.1 Method 1: Using Lead(IV) Acetate	165
20.5.1.3.5.2 Method 2: Using Oxone or Potassium Peroxymonosulfate	166
20.5.1.3.5.3 Method 3: Using Dioxygen	168
20.5.1.3.5.4 Method 4: Using Electrochemistry	169
20.5.1.4 Synthesis from Organometallic Compounds, Alkyl Halides, Primary Alcohols, or Ethers (Excluding Reactions with Carboxylic Acid Derivatives)	174
20.5.1.4.1 Alkoxycarbonylation of Organometallic Compounds	174
20.5.1.4.1.1 Method 1: Alkoxycarbonylation of Organolithium Compounds	174
20.5.1.4.1.2 Method 2: Alkoxycarbonylation of Organomagnesium Compounds	175
20.5.1.4.1.3 Method 3: Alkoxycarbonylation of Organotransition-Metal Compounds	176
20.5.1.4.2 Alkoxycarbonylation of Alkyl Halides	178
20.5.1.4.2.1 Method 1: Alkoxycarbonylation of Alkyl Halides Promoted by Acids	178
20.5.1.4.2.2 Method 2: Alkoxycarbonylation of Alkyl Halides Promoted by Transition-Metal Catalysts	179
20.5.1.4.2.3 Method 3: Alkoxycarbonylation of Alkyl Iodides Promoted by Photolysis	181
20.5.1.4.3 Oxidation of Primary Alcohols	181
20.5.1.4.3.1 Method 1: Oxidation by Halonium-Generating Combinations	182
20.5.1.4.3.2 Method 2: Oxidation by Chromium(IV) Oxide	183
20.5.1.4.3.3 Method 3: Transition-Metal-Catalyzed Oxidations	183
20.5.1.4.4 Oxidation of Ethers, Silyl Ethers, or Stannyl Ethers	184
20.5.1.4.4.1 Method 1: Oxidation of Ethers	185
20.5.1.4.4.1.1 Variation 1: Oxidation by Halonium-Generating Combinations	185
20.5.1.4.4.1.2 Variation 2: Oxidation by Stoichiometric Transition-Metal Reagents	185
20.5.1.4.4.1.3 Variation 3: Transition-Metal-Catalyzed Oxidation	186
20.5.1.4.4.2 Method 2: Oxidation of Silyl and Stannyl Ethers Using N-Bromosuccinimide	187
20.5.1.5 Synthesis from Alkenes (Excluding Reactions with Carboxylic Acid Derivatives)	192
20.5.1.5.1 Method 1: Oxidative C==C Bond Cleavage	192
20.5.1.5.2 Method 2: Hydroesterification with Carbon Monoxide (Reppe Carbonylation)	194
20.5.1.5.3 Method 3: Hydroesterification with Formate Esters	199
20.5.1.5.4 Method 4: Cross Metathesis with Conjugated Esters	203
20.5.1.5.5 Method 5: Synthesis via Hydroboration with Two-Carbon Homologation	205
20.5.1.5.6 Method 6: Addition of Acetate Esters to Alkenes	208
20.5.1.5.7 Method 7: Hydroacyloxylation	210
20.5.1.5.7.1 Variation 1: Markovnikov Hydroacyloxylation Using Carboxylic Acids	211
20.5.1.5.7.2 Variation 2: Anti-Markovnikov Hydroacyloxylation via Hydroboration	215
20.5.1.5.8 Method 8: Allylic Acyloxylation	215
20.5.1.5.8.1 Variation 1: Allylic Acyloxylation without Double-Bond Migration	215
20.5.1.5.8.2 Variation 2: Allylic Acyloxylation with Double-Bond Migration	218
20.5.1.5.9 Method 9: The Prévost Reaction	219
20.5.1.6 Synthesis by Rearrangement	224
20.5.1.6.1 Method 1: Baeyer--Villiger Oxidation	224
20.5.1.6.2 Method 2: Cope Rearrangement	228
20.5.1.6.2.1 Variation 1: Cope Rearrangement of Silyl Cyanohydrins	228
20.5.1.6.2.2 Variation 2: Cope Rearrangement of Divinylcyclopropanes	230
20.5.1.6.3 Method 3: Rearrangement of Vinylcyclopropanes	233
20.5.1.6.4 Method 4: Rearrangement of Ketene Acetals	236
20.5.1.6.4.1 Variation 1: Rearrangement of Ketene Acetals Derived from Ortho Esters (The Johnson Protocol)	237
20.5.1.6.4.2 Variation 2: Rearrangement of Ketene Acetals Derived from Selenoxides	240
20.5.1.6.5 Method 5: [2,3]-Wittig Rearrangement of a-(Alkenyloxy) Esters
242
20.5.1.6.5.1 Variation 1: Via Lithium Enolates	242
20.5.1.6.5.2 Variation 2: Via Tin, Titanium, and Zirconium Enolates	245
20.5.1.6.6 Method 6: [3,3] Rearrangements of Allylic Esters	246
20.5.1.6.7 Method 7: The Pummerer Rearrangement	249
20.5.1.6.8 Method 8: Palladium-Catalyzed Carbonylation with Rearrangement	251
20.5.1.6.9 Method 9: Favorskii Rearrangement	252
20.5.1.6.10 Method 10: Arndt--Eistert and Related Reactions	254
20.5.1.7 Synthesis with Retention of the Functional Group	260
20.5.1.7.1 Conjugate Addition of a,ß-Unsaturated Esters	260
20.5.1.7.1.1 Method 1: Addition of Organocopper Reagents	260
20.5.1.7.1.2 Method 2: Addition of Organoborane Reagents	262
20.5.1.7.1.3 Method 3: Addition of Nitroalkanes	265
20.5.1.7.1.4 Method 4: Hydrohalogenation Reactions of Substituted Allenoates	266
20.5.1.7.1.5 Method 5: Addition of Alkyl Radicals	267
20.5.1.7.1.6 Method 6: Addition of Organomanganese(II) Reagents	268
20.5.1.7.1.7 Method 7: Addition of Grignard Reagents	268
20.5.1.7.1.8 Method 8: Nickel(0)-Catalyzed Conjugate Additions	269
20.5.1.7.1.9 Method 9: Reductive C--C Bond Formation of a,ß-Unsaturated Esters	270
20.5.1.7.1.10 Method 10: Addition of Allyltrimethylsilane	271
20.5.1.7.2 Alkylations of Alkyl Alkanoates	272
20.5.1.7.2.1 Method 1: a-Alkylation	272
20.5.1.7.2.1.1 Variation 1: Alkylation with Strong Base and an Alkylating Agent	272
20.5.1.7.2.1.2 Variation 2: Metal-Complex-Catalyzed a-Alkylation	274
20.5.1.7.2.1.3 Variation 3: Michael Addition of Ester Enolates	275
20.5.1.7.2.2 Method 2: Deconjugate Alkylation	276
20.5.1.7.2.3 Method 3: Reductive Alkylation	277
20.5.1.7.2.4 Method 4: Ene Reaction	278
20.5.1.7.2.5 Method 5: Asymmetric Alkylation	279
20.5.1.7.3 Cross-Coupling Reactions Catalyzed by Transition-Metal Complexes	280
20.5.1.7.3.1 Method 1: Sonogashira Coupling	280
20.5.1.7.3.2 Method 2: Hydrovinylation	281
20.5.1.7.3.3 Method 3: Hydroformylation	282
20.5.1.7.3.4 Method 4: Other Palladium-Complex-Catalyzed Cross Couplings	283
20.5.1.7.4 Cleavage Reactions	286
20.5.1.7.4.1 Method 1: Cleavage of Oxalates	286
20.5.1.7.4.2 Method 2: Cleavage of Malonates by Decarboxylation	287
20.5.1.7.4.3 Method 3: Cleavage of a-Cyano Esters by Decyanation	288
20.5.1.7.4.4 Method 4: Cleavage of ß-Oxo Esters	290
20.5.1.7.5 Oxidation Reactions	291
20.5.1.7.5.1 Method 1: Ozonolysis	291
20.5.1.7.5.2 Method 2: Photooxygenation	292
20.5.1.7.6 Conjugate Reduction of a,ß-Unsaturated Esters	292
20.5.1.7.6.1 Method 1: Use of Aluminum Hydride Reducing Agents	293
20.5.1.7.6.2 Method 2: Use of Borohydride Reducing Agents	293
20.5.1.7.6.3 Method 3: Reduction Using Samarium(II) Iodide	295
20.5.1.7.6.4 Method 4: Use of Metals in Protic Solvents as Reducing Agents	296
20.5.1.7.6.5 Method 5: Hydrostannation	297
20.5.1.7.6.6 Method 6: Use of Hydrosilane Reducing Agents	297
20.5.1.7.6.7 Method 7: Use of Sodium Dithionite Reducing Agents	299
20.5.1.7.6.8 Method 8: Asymmetric Conjugate Reduction	299
20.5.1.7.7 Selective Reduction of Distant Multiple Bonds in Unsaturated Esters	300
20.5.1.7.7.1 Method 1: Reduction of Triple Bonds	301
20.5.1.7.7.2 Method 2: Reduction of Double Bonds	302
20.5.1.7.8 Chemoselective Hydrogenations	302
20.5.1.7.8.1 Method 1: Heterogeneous Hydrogenations	303
20.5.1.7.8.2 Method 2: Homogeneous Hydrogenations	304
20.5.1.7.8.3 Method 3: Asymmetric Hydrogenations	306
20.5.1.7.9 Synthesis from Lactones by Ring Opening	308
20.5.1.7.9.1 Method 1: Ring Opening under Basic Conditions	308
20.5.1.7.9.2 Method 2: Ring Opening under Acidic Conditions	309
20.5.1.7.9.3 Method 3: Enzyme-Catalyzed Ring Opening	310
20.5.1.7.10 Synthesis from Alkyl Formates	311
20.5.1.7.10.1 Method 1: Hydroesterifications Catalyzed by Transition-Metal Complexes	311
20.5.1.7.10.2 Method 2: Free-Radical Addition	312
20.5.1.7.10.3 Method 3: Palladium-Catalyzed Reaction with Nitrobenzene	313
20.5.1.7.10.4 Method 4: Carbonylation Reactions of Formates with Organic Halides	314
20.5.1.7.11 Isomerizations	314
20.5.1.7.11.1 Method 1: Deconjugation	314
20.5.1.7.11.2 Method 2: Other Isomerizations	316
20.5.1.7.12 Alkene Metathesis	317
20.5.1.7.12.1 Method 1: Metathesis with Tungsten-Based Catalysts	317
20.5.1.7.12.2 Method 2: Metathesis with Molybdenum-Based Catalysts	318
20.5.1.7.12.3 Method 3: Metathesis with Ruthenium-Based Catalysts	320
20.5.1.7.12.4 Method 4: Metathesis with Rhenium-Based Catalysts	322
20.5.1.7.13 Transesterification	323
20.5.1.7.13.1 Method 1: Transesterification without Catalysis	323
20.5.1.7.13.2 Method 2: Transesterification with Chemical Catalysis	324
20.5.1.7.13.2.1 Variation 1: By Brønsted Acids	324
20.5.1.7.13.2.2 Variation 2: By Lewis Acids	325
20.5.1.7.13.2.3 Variation 3: By Solid Acids	327
20.5.1.7.13.2.4 Variation 4: By Bases	328
20.5.1.7.13.3 Method 3: Transesterification with Enzymes	329
20.5.1.7.14 Kinetic Resolution	331
20.5.1.7.14.1 Method 1: Resolution with Enzymatic Catalysis	331
20.5.1.7.14.2 Method 2: Non-Enzymatic Resolution	333
20.5.2 Product Subclass 2: Arenedicarboxylic Acid Esters	344
20.5.2.1 Synthesis of Product Subclass 2	344
20.5.2.1.1 Method 1: Direct Esterification of Arenedicarboxylic Acids Using Alkyl Halides	344
20.5.2.1.2 Method 2: Direct Esterification of Arenedicarboxylic Acids and Anhydrides Using Alcohols	345
20.5.2.1.2.1 Variation 1: Using a Morpholinium Salt as Catalyst	345
20.5.2.1.2.2 Variation 2: Using Heteropolyacids as Catalysts	346
20.5.2.1.3 Method 3: Direct Esterification of Arenedicarboxylic Acids Using Pentafluorophenol and N,N'-Dicyclohexylcarbodiimide	347
20.5.2.1.4 Method 4: Synthesis of Arene-1,2-dicarboxylic Acid Esters by Diels--Alder Reaction Followed by Aromatization	347
20.5.2.1.4.1 Variation 1: From 2H-Pyran-2-ones	347
20.5.2.1.4.2 Variation 2: From 4-Nitrostyrene	349
20.5.2.1.4.3 Variation 3: From Substituted Benzo[c]furan	350
20.5.2.1.5 Methods 5: Miscellaneous Methods	350
20.5.3 Product Subclass 3: Butenedioic and Butynedioic Acid Esters	354
20.5.3.1 Synthesis of Product Subclass 3	354
20.5.3.1.1 Method 1: Anhydride Cleavage	354
20.5.3.1.1.1 Variation 1: Solvolysis of Maleic Anhydride	354
20.5.3.1.1.2 Variation 2: Using Lactam Acetals	355
20.5.3.1.2 Method 2: Carbenoid Dimerization	356
20.5.3.1.2.1 Variation 1: Ruthenium-Mediated Reactions	356
20.5.3.1.2.2 Variation 2: Rhodium-Mediated Reactions	358
20.5.3.1.2.3 Variation 3: Copper-Mediated Reactions	358
20.5.3.1.3 Method 3: Phosphorus-Based Alkenations	359
20.5.3.1.3.1 Variation 1: From Thiiranes	359
20.5.3.1.3.2 Variation 2: From Lithiophosphoranes	361
20.5.3.1.4 Method 4: 1,4-Addition of Alcohols	362
20.5.3.1.4.1 Variation 1: Organic Base Mediated Reactions	362
20.5.3.1.4.2 Variation 2: Titanium-Mediated Reactions	362
20.5.3.1.4.3 Variation 3: Lead-Mediated Reactions	363
20.5.3.1.4.4 Variation 4: Silver-Mediated Reactions	364
20.5.3.1.5 Method 5: Elimination Protocols	365
20.5.3.1.5.1 Variation 1: From Aspartate Esters	365
20.5.3.1.5.2 Variation 2: From Monohalosuccinic Acid Esters	366
20.5.3.1.5.3 Variation 3: From Hydroxysuccinic Acid Esters	367
20.5.3.1.5.4 Variation 4: From Dibromosuccinic Acid Esters with Dimethylformamide	367
20.5.3.1.5.5 Variation 5: From Tartrates via Phosphinate Activation	368
20.5.3.1.5.6 Variation 6: From Tartrates via Cyclic Sulfates	369
20.5.3.1.5.7 Variation 7: From Bromosuccinic Acid Esters	370
20.5.3.1.5.8 Variation 8: From Dibromosuccinates with Sodium Dithionite	371
20.5.3.1.5.9 Variation 9: From vic-Diols via 1,3-Dioxolanes	372
20.5.3.1.5.10 Variation 10: From vic-Diols via Phosphonium Sulfates	373
20.5.3.1.5.11 Variation 11: From vic-Diols with Sodium Sulfide	375
20.5.3.1.5.12 Variation 12: From vic-Diols via Thermal Elimination	375
20.5.3.1.6 Method 6: Semihydrogenation	376
20.5.3.1.6.1 Variation 1: Using Homogeneous Palladium Catalysts	376
20.5.3.1.6.2 Variation 2: Using Hydrosilane Reagents	377
20.5.3.1.6.3 Variation 3: Using Nickel Boride Catalysts	378
20.5.3.1.6.4 Variation 4: Using a Polymer-Supported Palladium Catalyst	379
20.5.3.1.6.5 Variation 5: Using a Rhodium Hydride Complex	379
20.5.3.1.6.6 Variation 6: Using an Indium Hydride Complex	380
20.5.3.1.7 Methods 7: Other Methods	381
20.5.3.1.7.1 Variation 1: Phosphine Additions to Butynedioates	381
20.5.3.1.7.2 Variation 2: Carbene Additions to Maleic Anhydride Derivatives	382
20.5.4 Product Subclass 4: Alkanedioic Acid Esters	384
20.5.4.1 Synthesis of Product Subclass 4	384
20.5.4.1.1 Method 1: Esterification of Oxalic Acid by the Fischer Method	384
20.5.4.1.2 Method 2: Oxalate Esters by Nucleophilic Acyl Substitution on Activated Oxalyl Derivatives	385
20.5.4.1.2.1 Variation 1: From Oxalyl Chloride	385
20.5.4.1.2.2 Variation 2: From Ethyl Cyano(oxo)acetate	385
20.5.4.1.3 Method 3: Oxalate Esters by Oxidative Methods	386
20.5.4.1.3.1 Variation 1: Palladium-Mediated Oxidative Coupling of Carbon Monoxide	386
20.5.4.1.3.2 Variation 2: Oxidative Cleavage of 2-Chlorobuta-1,3-diene	387
20.5.4.1.4 Method 4: Esterification of Malonic Acids	387
20.5.4.1.4.1 Variation 1: Using Isobutene	387
20.5.4.1.4.2 Variation 2: Via the Monoacid Chloride	388
20.5.4.1.4.3 Variation 3: Via Mixed Carbonic Anhydrides	389
20.5.4.1.5 Method 5: Malonate Esters by Alkylation of Malonate Derivatives	390
20.5.4.1.5.1 Variation 1: Via Monoalkylation of Malonate Diesters	390
20.5.4.1.5.2 Variation 2: Phase-Transfer-Catalyzed Dialkylation of Malonates	391
20.5.4.1.5.3 Variation 3: Intramolecular Cyclization of .-(Bromoalkyl)malonates	392
20.5.4.1.5.4 Variation 4: Transition-Metal-Mediated Alkylations	393
20.5.4.1.5.5 Variation 5: Alkylation--Decarboxylation of Methanetricarboxylates	393
20.5.4.1.5.6 Variation 6: Via Alkylation of Meldrum's Acid	394
20.5.4.1.6 Method 6: Malonate Esters by Acylation of Malonate Derivatives	395
20.5.4.1.6.1 Variation 1: Via Ethoxymagnesium Malonates	395
20.5.4.1.6.2 Variation 2: C-Acylation Using Magnesium Oxide	396
20.5.4.1.6.3 Variation 3: C-Acylation Using Soft Enolization	397
20.5.4.1.7 Method 7: Malonate Esters by Conjugate Additions to Malonate Derivatives	398
20.5.4.1.7.1 Variation 1: Reduction of Alkylidenemalonates with Sodium Cyanoborohydride	398
20.5.4.1.7.2 Variation 2: Grignard Additions to Alkylidenemalonates	398
20.5.4.1.7.3 Variation 3: Phase-Transfer-Catalyzed Michael Addition of Malonate Enolates	399
20.5.4.1.8 Method 8: Malonate Esters by Knoevenagel Condensation of Malonates	400
20.5.4.1.8.1 Variation 1: With Acetaldehyde and Acetic Anhydride	400
20.5.4.1.8.2 Variation 2: With Paraformaldehyde and Copper(II) Acetate	400
20.5.4.1.8.3 Variation 3: From Pyrolysis of Malonate Diels--Alder Adducts	401
20.5.4.1.9 Method 9: Malonate Esters by Claisen Condensations with Oxalic Acid Esters	402
20.5.4.1.10 Method 10: Malonate Esters by Arylation of Malonate Derivatives	403
20.5.4.1.10.1 Variation 1: Via Electrophilic Aromatic Substitution	403
20.5.4.1.10.2 Variation 2: Via Nucleophilic Aromatic Substitution on Malonyl--Iron--Arene Complexes	405
20.5.4.1.11 Method 11: Malonate Esters by Addition of Allylsilanes to Activated Cyclopropanes	405
20.5.4.1.12 Method 12: Malonate Esters by Dichlorination of Malonates with Trifluoromethanesulfonyl Chloride	406
20.5.4.1.13 Method 13: Esterification of Succinic Acid	407
20.5.4.1.14 Method 14: Succinate Esters by Reduction of Butenedioates	407
20.5.4.1.14.1 Variation 1: Lewis Acid Mediated Reduction of Maleates	407
20.5.4.1.14.2 Variation 2: Ruthenium-Mediated Hydrogenation of 2-Methylenesuccinate Esters	408
20.5.4.1.14.3 Variation 3: Rhodium-Mediated Hydrogenation of 2-Methylenesuccinate Esters	409
20.5.4.1.15 Method 15: Succinate Esters by Alkene Dimerization	410
20.5.4.1.15.1 Variation 1: Radical-Based Methods	410
20.5.4.1.15.2 Variation 2: Oxidative Dimerization of Titanium Enolates	411
20.5.4.1.15.3 Variation 3: Oxidative Dimerization of Organocuprates	412
20.5.4.1.16 Method 16: Succinate Esters by Rearrangement Reactions	413
20.5.4.1.16.1 Variation 1: Ring Opening of Cyclopropanes	413
20.5.4.1.16.2 Variation 2: Malonate Displacements	414
20.5.4.1.16.3 Variation 3: Allylmalonate Rearrangement	415
20.5.4.1.17 Method 17: Succinate Esters by Carbonylation	416
20.5.4.1.17.1 Variation 1: Dicarbonylation of But-2-enes	416
20.5.4.1.17.2 Variation 2: Dicarbonylation of Terminal Alkenes and Cycloalkenes	417
20.5.4.1.17.3 Variation 3: Monocarbonylation of Acrylates	419
20.5.4.1.17.4 Variation 4: From Allylic Carbonates	420
20.5.4.1.18 Method 18: Succinate Esters by Conjugate Additions	420
20.5.4.1.18.1 Variation 1: Reaction of Thiols with Butenedioates	420
20.5.4.1.18.2 Variation 2: Reaction of Enamines with Nitroalkenes	421
20.5.4.1.18.3 Variation 3: Reaction of Cyanohydrins with Butenedioates	422
20.5.4.1.19 Method 19: Succinate Esters by Stobbe Condensations	423
20.5.4.1.20 Method 20: Succinate Esters by a-Alkylation of Succinoyl Derivatives	424
20.5.4.1.20.1 Variation 1: Using an Organometallic Auxiliary	424
20.5.4.1.20.2 Variation 2: Using Malate Esters	425
20.5.4.1.21 Method 21: Succinate Esters by Asymmetric Nucleophilic Addition Using a Chiral Ketone Auxiliary	426
20.5.4.1.22 Method 22: Succinate Esters by Stereoselective [2,3]-Wittig Rearrangement	427
20.5.4.1.23 Method 23: Succinate Esters by Asymmetric Alkylation Using N-Acyloxazolidinones (Evans Asymmetric Alkylation)	428
20.5.4.1.23.1 Variation 1: Application to the Synthesis of a Pharmaceutical Agent	429
20.5.4.1.24 Method 24: Succinate Esters by Aldol Approaches	430
20.5.4.1.24.1 Variation 1: Using Chiral Imines	430
20.5.4.1.24.2 Variation 2: 2-Substituted 2-Hydroxysuccinates Using a Stoichiometric Chiral Tin Lewis Acid	431
20.5.4.1.24.3 Variation 3: 2,3-Disubstituted 2-Hydroxysuccinates Using a Stoichiometric Chiral Tin Lewis Acid	432
20.5.4.1.24.4 Variation 4: Using Chiral N-Acylhydrazones	433
20.5.4.1.24.5 Variation 5: Using a Catalytic Chiral Titanium Lewis Acid	434
20.5.4.1.24.6 Variation 6: Using a Catalytic Chiral Copper Lewis Acid	435
20.5.4.1.24.7 Variation 7: Use of a Fluorous Lewis Acid Catalyst	436
20.5.4.1.24.8 Variation 8: Use of a Catalytic Tin Lewis Acid	438
20.5.4.1.24.9 Variation 9: Application of a Chiral Tin Lewis Acid in Total Synthesis	439
20.5.4.1.24.10 Variation 10: Use of a Cationic Scandium Lewis Acid	440
20.5.5 Product Subclass 5: Alkynyl Alkanoates	444
20.5.5.1 Synthesis of Product Subclass 5	444
20.5.5.1.1 Method 1: Metalation and Rearrangement of a,a-Dihalo Ketones (Alkynolate Anions)	444
20.5.5.1.2 Method 2: Reaction of Carboxylic Acids with Alkynyliodonium Salts	445
20.5.5.1.2.1 Variation 1: Using Preformed Alkynyliodonium Ions	445
20.5.5.1.2.2 Variation 2: Using (Diacyliodo)arenes	446
20.5.6 Product Subclass 6: Aryl Alkanoates	448
20.5.6.1 Synthesis of Product Subclass 6	449
20.5.6.1.1 Method 1: Acylation of Phenols	449
20.5.6.1.1.1 Variation 1: Direct Acylation	449
20.5.6.1.1.2 Variation 2: Lewis Acid Catalyzed Acylation	454
20.5.6.1.1.3 Variation 3: Lewis Base Catalyzed Acylation	456
20.5.6.1.2 Method 2: Oxidation of Arenes	457
20.5.6.1.2.1 Variation 1: Acyl Peroxide Mediated Oxidation	457
20.5.6.1.2.2 Variation 2: Lead(IV) Acetate Mediated Oxidation	459
20.5.6.1.3 Method 3: Displacement of Diazonium Groups by Nucleophiles (The Sandmeyer Reaction)	459
20.5.7 Product Subclass 7: Alkenyl Alkanoates	462
20.5.7.1 Synthesis of Product Subclass 7	466
20.5.7.1.1 Method 1: O-Acylation of Enolates	466
20.5.7.1.1.1 Variation 1: Kinetic Deprotonation	466
20.5.7.1.1.2 Variation 2: Fluoride-Catalyzed O-Acylation of Enolates	469
20.5.7.1.1.3 Variation 3: O-Acylation of Enolates and Enols Generated under Equilibrating Conditions	471
20.5.7.1.2 Method 2: O-Acylation of Aldehyde Enolates Derived from Alkynoate Anions	473
20.5.7.1.3 Method 3: Metal-Catalyzed Alkoxycarbonylation of Alkynes	474
20.5.7.1.4 Method 4: Cross-Coupling of Alkenylmercury Halides or Alkenyl Halides with Metal Acetate Salts	481
20.5.7.1.5 Method 5: Coupling of Fischer Carbenes with Acid Chlorides	483
20.5.7.1.6 Method 6: Alkenation Reactions	483
20.5.8 Product Subclass 8: 2-Oxo- and 2-Imino-Substituted Alkanoic Acid Esters, and Related Compounds	488
20.5.8.1 Synthesis of Product Subclass 8	488
20.5.8.1.1 Method 1: Esterification of 2-Heteroatom-Substituted Acids	488
20.5.8.1.2 Method 2: Hydrolysis of 2-Heteroatom-Substituted Esters	491
20.5.8.1.3 Method 3: Alcoholysis of 2-Heteroatom-Substituted Nitriles	494
20.5.8.1.4 Method 4: Oxidation Reactions	495
20.5.8.1.4.1 Variation 1: Oxidation of a-Hydroxy Esters	495
20.5.8.1.4.2 Variation 2: Oxidation of a-Diazo Esters	497
20.5.8.1.4.3 Variation 3: Oxidation of 3-Oxo-2-(triphenylphosphoranylidene)propanoates	498
20.5.8.1.4.4 Variation 4: Oxidation of 2-Alkylidene Esters	499
20.5.8.1.5 Method 5: Addition of Organometallic Reagents to Oxalates	500
20.5.8.1.6 Method 6: Friedel--Crafts Acylation of Buta-1,3-dienes, Arenes, and Hetarenes	503
20.5.8.1.7 Method 7: Sigmatropic Rearrangements	505
20.5.8.1.7.1 Variation 1: Claisen Rearrangement of Allyl Vinyl Ethers	505
20.5.8.1.7.2 Variation 2: Stevens Rearrangement of N,N-Dimethyl-N-(phenylethynyl)glycinium Bromides	506
20.5.8.1.8 Method 8: Hetero-Diels--Alder Reactions	507
20.5.8.1.9 Method 9: Aldol Condensations	507
20.5.9 Product Subclass 9: 2,2-Diheteroatom-Substituted Alkanoic Acid Esters	512
20.5.9.1 Synthesis of Product Subclass 9	512
20.5.9.1.1 Method 1: Esterification of 2,2-Diheteroatom-Substituted Acids	512
20.5.9.1.2 Method 2: Synthesis by Acetal Formation	514
20.5.9.1.2.1 Variation 1: Formation of Acetals and Hemiacetals	514
20.5.9.1.2.2 Variation 2: Formation of a,a-Diamino Esters	516
20.5.9.1.2.3 Variation 3: Formation of Thioacetals	517
20.5.9.1.3 Method 3: Alcoholysis of 2,2-Diheteroatom-Substituted Nitriles	517
20.5.9.1.4 Method 4: Oxidation of Alkene Derivatives	518
20.5.9.1.5 Method 5: Synthesis by Nucleophilic Attack of the a-Carbon of Esters	520
20.5.9.1.5.1 Variation 1: Nucleophilic Substitution at the a-Carbon of 2,2-Diheteroatom-Substituted Esters	520
20.5.9.1.5.2 Variation 2: Nucleophilic Substitution at the a-Carbon of Diesters and ß-Oxo Esters	521
20.5.9.1.5.3 Variation 3: Metal-Mediated C--C Bond Formation	522
20.5.9.1.6 Method 6: Radical-Mediated Transformations of 2-Halo-Substituted Esters	523
20.5.9.1.7 Method 7: 1,3-Allylic Rearrangement of a Chiral Acetal	524
20.5.9.1.8 Method 8: Rearrangement of (ortho-Nitroarylidene)malonates	524
20.5.10 Product Subclass 10: 2-Aminoalkanoic Acid Esters (a-Amino Acid Esters)	528
20.5.10.1 Synthesis of Product Subclass 10	528
20.5.10.1.1 a,ß-Didehydroamino Acid Esters	528
20.5.10.1.1.1 Synthesis of a,ß-Didehydroamino Acid Esters through Palladium(0)-Catalyzed Cross-Coupling Reactions	528
20.5.10.1.1.1.1 Method 1: Suzuki Coupling of ß-Bromoamidoacrylates with Aryl- and Vinylboronic Acids	528
20.5.10.1.1.1.2 Method 2: Heck Coupling of Amidoacrylates with Aryl and Vinyl Halides	529
20.5.10.1.1.2 Synthesis of a,ß-Didehydroamino Esters through Elimination	530
20.5.10.1.1.2.1 Method 1: Erlenmeyer Condensation	530
20.5.10.1.1.2.2 Method 2: Horner--Emmons Condensation	531
20.5.10.1.2 2-Aminoalkanoic Acid Esters	532
20.5.10.1.2.1 Introduction of the Side Chain: Alkylation of Glycine and Related Chiral Enolates	533
20.5.10.1.2.1.1 Method 1: Alkylation of Chiral Cyclic Enolates	533
20.5.10.1.2.1.1.1 Variation 1: Alkylation of Chiral Bis-lactim Ethers	533
20.5.10.1.2.1.1.2 Variation 2: Alkylation of Chiral Oxazinones	535
20.5.10.1.2.1.2 Method 2: Alkylation of Chiral Acyclic Schiff Bases	536
20.5.10.1.2.1.3 Method 3: Alkylation Utilizing Chiral Phase-Transfer Reagents	538
20.5.10.1.2.1.4 Method 4: Metal-Mediated Glycine Enolate Alkylation	540
20.5.10.1.2.1.4.1 Variation 1: Palladium-Catalyzed Allylation of Glycine Derivatives	540
20.5.10.1.2.1.4.2 Variation 2: Gold-Catalyzed Aldol Reactions	543
20.5.10.1.2.1.4.3 Variation 3: Titanium-Mediated Aldol Reactions	544
20.5.10.1.2.1.4.4 Variation 4: Aluminum--Salen-Catalyzed Aldol Reactions of 5-Alkoxyoxazoles	546
20.5.10.1.2.2 Introduction of the a-Amino Group: Nucleophilic Amination	547
20.5.10.1.2.2.1 Method 1: Intermolecular Nucleophilic Addition to Chiral Epoxides	547
20.5.10.1.2.2.2 Method 2: Intramolecular Nucleophilic Addition to Epoxides	548
20.5.10.1.2.2.3 Method 3: Nucleophilic Displacement of Halides	550
20.5.10.1.2.2.4 Method 4: Nucleophilic Displacement of Sulfonic Esters and Cyclic Sulfates	551
20.5.10.1.2.2.4.1 Variation 1: Displacement of Trifluoromethanesulfonates	551
20.5.10.1.2.2.4.2 Variation 2: Opening Cyclic Sulfates	552
20.5.10.1.2.2.5 Method 5: Mitsunobu Displacement of an a-Hydroxy Group	553
20.5.10.1.2.2.6 Method 6: Nucleophilic Addition to p-Allylpalladium Intermediates	553
20.5.10.1.2.3 Introduction of the a-Amino Group: Electrophilic Amination of Enolates	555
20.5.10.1.2.3.1 Method 1: Proline Organocatalysis	555
20.5.10.1.2.4 Introduction of the a-Hydrogen: Asymmetric Hydrogenation of a,ß-Didehydroamino Acid Esters	556
20.5.10.1.2.4.1 Method 1: Homogeneous Catalysis	556
20.5.10.1.2.4.1.1 Variation 1: Cationic Rhodium Complexes of Chiral C2-Symmetric Bisphosphines	559
20.5.10.1.2.4.1.2 Variation 2: Cationic Rhodium Complexes of Chiral C2-Symmetric Bisphosphinites	560
20.5.10.1.2.4.1.3 Variation 3: Cationic Rhodium Complexes of P-Chirogenic Phosphines	561
20.5.10.1.2.5 Introduction of the a-Hydrogen: Asymmetric Michael Addition	561
20.5.10.1.2.5.1 Method 1: Enantioselective Michael Addition--Hydrogen Atom Transfer	561
20.5.10.1.2.5.2 Method 2: Diastereoselective Organocuprate Michael Addition to Chiral Piperazine-2,5-dione Acceptors	562
20.5.10.1.2.6 Introduction of Carboxylate: Asymmetric Addition of Nitriles to Imines (Strecker Synthesis)	564
20.5.10.1.2.6.1 Method 1: Chiral Binuclear Zirconium-Complex-Catalyzed Strecker Synthesis	564
20.5.10.1.2.6.2 Method 2: Chiral Aluminum--Salen Complex Catalyzed Strecker Synthesis	565
20.5.10.1.2.7 Introduction of the Side Chain: Asymmetric Addition to Imino Esters	567
20.5.10.1.2.7.1 Method 1: Proline-Catalyzed Mannich Additions to Imino Esters	567
20.5.10.1.2.7.2 Method 2: Copper-Catalyzed Alkylations of Imino Esters	568
20.5.10.1.2.7.3 Method 3: Catalytic Asymmetric Mannich Additions to Imino Esters	568
20.5.10.1.2.7.4 Method 4: Catalytic Asymmetric Aza-Henry Addition to Imino Esters	569
20.5.10.1.2.7.5 Method 5: Palladium-Catalyzed Silyl Enol Ether Additions of Imino Esters	571
20.5.10.1.2.7.6 Method 6: Catalytic Asymmetric Aromatic Additions to Imino Esters	572
20.5.10.1.2.7.7 Method 7: Organometallic Additions to Chiral Imino Esters	573
20.5.10.1.2.7.8 Method 8: Mannich-Type Reaction of Electron-Rich Aromatic Compounds with Chiral Imino Lactones	574
20.5.10.1.2.7.9 Method 9: Rhodium-Catalyzed Addition of Arylboronic Acids to N-(tert-Butylsulfinyl)imino Esters	575
20.5.10.1.2.8 Introduction of the Side Chain: Diels--Alder Cycloaddition Reactions	577
20.5.10.1.2.8.1 Method 1: Catalytic Asymmetric Diels--Alder Addition to Chiral Imino Esters	577
20.5.10.1.2.8.2 Method 2: Asymmetric Diels--Alder Addition to Chiral Imino Esters	Chiral Menthyl Derivatives	578
20.5.10.1.2.8.3 Method 3: Asymmetric Diels--Alder Addition to Chiral Imino Esters	Chiral 1-Phenylethylamine Derivatives	578
20.5.10.1.2.9 Introduction of the a-Nitrogen: Sigmatropic Rearrangements	579
20.5.10.1.2.9.1 Method 1: Rearrangement of Allylic Trichloroacetimidates	579
20.5.10.1.2.9.1.1 Variation 1: Thermal Rearrangement of Chiral Allylic Trichloroacetimidates	580
20.5.10.1.2.9.1.2 Variation 2: Enantioselective Palladium-Catalyzed Rearrangement of Prochiral Allylic Trichloroacetimidates	581
20.5.10.1.2.10 Addition of the Carboxylate Group: Rearrangements	582
20.5.10.1.2.10.1 Method 1: Photolysis of Chromium--Carbene Complexes	582
20.5.10.1.3 a-Alkyl-a-aminoalkanoic Acid Esters	583
20.5.10.1.3.1 Introduction of the Side Chain: Alkylation of Chiral Amino Acid Enolates	584
20.5.10.1.3.1.1 Method 1: Alkylation of Bis-lactim Ethers	584
20.5.10.1.3.1.2 Method 2: Alkylation of Schiff Bases	585
20.5.10.1.3.1.2.1 Variation 1: Alkylation of Galactodialdehyde Aldimines	585
20.5.10.1.3.1.2.2 Variation 2: Alkylation of Camphor-Derived Sultams	586
20.5.10.1.3.1.3 Method 3: Transition-Metal-Catalyzed Asymmetric Allylic Alkylation of Azlactones	587
20.5.10.1.3.1.3.1 Variation 1: Palladium-Catalyzed Asymmetric Allylic Alkylation of Azlactones	588
20.5.10.1.3.1.3.2 Variation 2: Molybdenum-Catalyzed Asymmetric Allylic Alkylation of Azlactones	589
20.5.10.1.3.2 Introduction of the Side Chain: Rearrangements	590
20.5.10.1.3.2.1 Method 1: Rearrangement of O-Acylated Azlactones	590
20.5.10.1.3.3 Introduction of the a-Amino Group: Rearrangement of a,a-Dialkyl-ß-carbonyl Carboxylic Acid Esters	591
20.5.10.1.3.3.1 Method 1: Curtius Rearrangement of a,a-Dialkyl ß-Ester Carboxylic Acids	592
20.5.10.1.3.3.2 Method 2: Hofmann Rearrangement of a,a-Dialkyl-ß-amido Esters	592
20.5.10.1.3.3.3 Method 3: Schmidt Rearrangement of ß-Oxo Esters	593
20.5.10.1.3.3.4 Method 4: Beckmann Rearrangement of ß-Oxime Esters	594
20.5.11 Product Subclass 11: 2-Heteroatom-Substituted Alkanoic Acid Esters	600
20.5.11.1 Synthesis of Product Subclass 11	600
20.5.11.1.1 2-Haloalkanoates	600
20.5.11.1.1.1 2-Fluoroalkanoates	600
20.5.11.1.1.1.1 Method 1: Electrophilic Fluorination of Alkanoates	601
20.5.11.1.1.1.1.1 Variation 1: Fluorination with N-Fluorobis(trifluoromethylsulfonyl)amine	601
20.5.11.1.1.1.1.2 Variation 2: Fluorination with 2-Fluoro-1,3,2-benzodithiazole 1,1,3,3-Tetraoxide	602
20.5.11.1.1.1.1.3 Variation 3: Catalytic Asymmetric Fluorination of a-Cyano Esters by Treatment with Chiral Palladium Complexes and N-Fluorobis(phenylsulfonyl)amine	603
20.5.11.1.1.1.1.4 Variation 4: Catalytic Asymmetric Fluorination of ß-Oxo Esters	604
20.5.11.1.1.1.2 Method 2: Kinetic Enzymatic Resolution of Racemic 2-Fluoroalkanoates	604
20.5.11.1.1.2 2-Chloroalkanoates	605
20.5.11.1.1.2.1 Method 1: Chlorination of Ester Enolates	605
20.5.11.1.1.2.1.1 Variation 1: Catalytic Asymmetric Chlorination of ß-Oxo Esters Using Chiral Titanium Lewis Acids	606
20.5.11.1.1.2.1.2 Variation 2: Tandem Chlorination/Esterification of Acid Halides	606
20.5.11.1.1.2.2 Method 2: Nucleophilic Displacement of a Hydroxy Group	608
20.5.11.1.1.3 2-Bromoalkanoates	608
20.5.11.1.1.3.1 Method 1: Electrophilic Bromination of Carbon Nucleophiles	609
20.5.11.1.1.3.1.1 Variation 1: Catalytic Asymmetric Bromination with Chiral Bis(dihydrooxazole)--Copper(II) Complexes	609
20.5.11.1.1.3.1.2 Variation 2: Asymmetric Tandem Bromination/Esterification of Acid Chlorides	610
20.5.11.1.1.4 2-Iodoalkanoates	610
20.5.11.1.1.4.1 Method 1: Formation of 2-Iodoalkanoates with N-Iodosuccinimide under Microwave Conditions	611
20.5.11.1.2 2-Hydroxyalkanoates	611
20.5.11.1.2.1 Method 1: Catalytic Asymmetric Hydrogenation of 2-Oxoalkanoates	611
20.5.11.1.2.1.1 Variation 1: Homogeneous Catalytic Asymmetric Hydrogenation of 2-Oxoalkanoates	612
20.5.11.1.2.1.2 Variation 2: Heterogeneous Catalytic Asymmetric Hydrogenation of 2-Oxoalkanoates	613
20.5.11.1.2.1.3 Variation 3: Examples of Industrially Important Enantioselective Hydrogenations	614
20.5.11.1.2.2 Method 2: Catalytic Asymmetric C--C Bond-Forming Reactions	615
20.5.11.1.2.2.1 Variation 1: Asymmetric Alkylation of 2-Hydroxyacetates	616
20.5.11.1.2.2.2 Variation 2: Enantioselective Addition of Silyl Enol Ethers to Ethyl Glyoxylate and 2-Oxoalkanoates	617
20.5.11.1.2.3 Method 3: Asymmetric Oxidations	618
20.5.11.1.2.3.1 Variation 1: Oxidation of Enolates with Oxaziridines	618
20.5.11.1.2.3.2 Variation 2: Sharpless Catalytic Asymmetric Dihydroxylation of a,ß-Unsaturated Esters	619
20.5.11.1.2.3.3 Variation 3: Synthesis of the Taxol Side Chain Using the Sharpless Catalytic Asymmetric Aminohydroxylation of Cinnamate Esters	621
20.5.11.1.2.4 Method 4: Resolution	621
20.5.11.1.3 2-Alkoxyalkanoates	623
20.5.11.1.3.1 Method 1: O-Alkylation of a 2-Hydroxyalkanoate	623
20.5.11.1.3.2 Method 2: 2-Alkoxyalkanoates by C--C Bond-Forming Reactions	623
20.5.11.1.4 2,3-Epoxyalkanoates	624
20.5.11.1.4.1 Method 1: Asymmetric Epoxidation of a,ß-Unsaturated Esters with Chiral Dioxiranes	625
20.5.11.1.4.2 Method 2: Chiral Manganese(III)--Salen Catalyzed Enantioselective Epoxidation of cis-a,ß-Unsaturated Esters	626
20.5.11.1.4.3 Method 3: Catalytic Enantioselective Epoxidation of a,ß-Unsaturated Esters Using a Lanthanide Lewis Acid Catalyst and tert-Butyl Hydroperoxide	626
20.5.11.1.5 2-Sulfanylalkanoates	627
20.5.11.1.5.1 Method 1: Sulfanylation of Enolates	628
20.5.11.1.5.1.1 Variation 1: Sulfanylation of Ester Enolates	628
20.5.11.1.5.1.2 Variation 2: Catalytic Enantioselective Sulfanylation of ß-Oxo Esters	628
20.5.11.1.5.2 Method 2: Nucleophilic Displacement with Thiolates	629
20.5.11.1.5.2.1 Variation 1: Direct Displacement of a Chiral Methanesulfonate	629
20.5.11.1.5.2.2 Variation 2: Dynamic Resolution of 2-Bromoalkanoic Acid N-Methylpseudoephedrine Esters with Triphenylmethanethiol	630
20.5.11.1.6 2-Selanylalkanoates	631
20.5.11.1.6.1 Method 1: Selanylation of Enolates	631
20.5.11.1.6.2 Method 2: Synthesis Using the Selenide Anion	632
20.5.11.1.6.2.1 Variation 1: Opening of Epoxides	632
20.5.11.1.6.2.2 Variation 2: Synthesis of Selenides by Nucleophilic Substitution	632
20.5.11.1.7 2-Tellanylalkanoates	633
20.5.11.1.7.1 Method 1: Synthesis Using the Telluride Anion	633
20.5.11.1.7.2 Method 2: Synthesis from Iodotelluride	634
20.5.12 Product Subclass 12: Alk-2-ynoic Acid Esters	640
20.5.12.1 Synthesis of Product Subclass 12	640
20.5.12.1.1 Method 1: Esterification of Alk-2-ynoic Acids or Derivatives	640
20.5.12.1.1.1 Variation 1: Direct Esterification of Alk-2-ynoic Acids	640
20.5.12.1.1.2 Variation 2: Alkylation of Alk-2-ynoic Acids or Their Salts	646
20.5.12.1.1.3 Variation 3: Alcoholysis of Alk-2-ynoic Acid Derivatives	650
20.5.12.1.2 Method 2: Carboxylation of Alk-1-ynes	652
20.5.12.1.2.1 Variation 1: Carboxylation of Alk-1-ynes by Deprotonation--Carboxylation	652
20.5.12.1.2.2 Variation 2: Carboxylation of Lithium Acetylides Derived from 1,1-Dihaloalkenes Produced from Aldehydes by Corey--Fuchs Alkenation	656
20.5.12.1.2.3 Variation 3: Carboxylation of Lithium Acetylides Derived from 1-Haloalkenes	658
20.5.12.1.2.4 Variation 4: Palladium-Catalyzed Carboxylation of Alk-1-ynes with Chloroformates	658
20.5.12.1.2.5 Variation 5: Palladium-Catalyzed Carboxylation of Alk-1-ynes with Carbon Monoxide and Alcohols	659
20.5.12.1.2.6 Variation 6: Copper-Catalyzed Carboxylation of Alk-1-ynes with Carbon Dioxide and Alkyl Bromides	661
20.5.12.1.3 Method 3: Synthesis from Alk-2-enoic Acid Esters by Bromination--Dehydrobromination	661
20.5.12.1.4 Method 4: Using Wittig-Type Reactions	662
20.5.12.1.4.1 Variation 1: Reaction of [(Alkoxycarbonyl)methylene]triphenylphospho-ranes with Acyl Chlorides, Anhydrides, or Carboxylic Acids	662
20.5.12.1.4.2 Variation 2: Reaction of [(Ethoxycarbonyl)iodomethyl]triphenyl-phosphonium Iodide with Aldehydes	666
20.5.12.1.5 Method 5: Modifications of Propynoic Acid Esters or Derivatives	667
20.5.12.1.5.1 Variation 1: Coupling of Propynoic Acid Esters	667
20.5.12.1.5.2 Variation 2: Coupling of Bromopropynoic Acid Esters	671
20.5.12.1.5.3 Variation 3: Addition of Metalated Propynoic Acid Esters to Electrophiles	672
20.5.12.1.6 Method 6: Dehydration of ß-Oxo Esters	676
20.5.12.1.7 Method 7: Deaminative Dehydration of a-Diazo-ß-hydroxy Esters Derived from Aldehydes	676
20.5.13 Product Subclass 13: Arenecarboxylic Acid Esters	682
20.5.13.1 Synthesis of Product Subclass 13	682
20.5.13.1.1 Method 1: Friedel--Crafts Acylation	682
20.5.13.1.2 Method 2: Oxidation of Benzylic Ethers	683
20.5.13.1.3 Method 3: Radical Benzyloxylation	684
20.5.13.1.4 Method 4: Metalation/Carbonylation of Arenes	685
20.5.13.1.4.1 Variation 1: Direct Metalation	685
20.5.13.1.4.2 Variation 2: Reductive Metalation of Haloarenes	686
20.5.13.1.4.3 Variation 3: Lithium--Halogen Exchange with Haloarenes	687
20.5.13.1.4.4 Variation 4: Metalation of Tricarbonylchromium--.6-Arene Complexes	688
20.5.13.1.5 Method 5: Palladium-Mediated C--H Activation and Carbonylation	689
20.5.13.1.6 Method 6: Palladium-Catalyzed Carbonylation of Main-Group Arylmetal Species	690
20.5.13.1.6.1 Variation 1: Stille Coupling of Alkyl Chloroformates with Arylstannanes	690
20.5.13.1.6.2 Variation 2: Carbonylation of Arylboranes with Carbon Monoxide	691
20.5.13.1.7 Method 7: Transition-Metal-Catalyzed Carbonylation of Haloarenes	691
20.5.13.1.8 Method 8: Construction of the Aromatic Ring by Anionic Methods	692
20.5.13.1.8.1 Variation 1: Anionic [3 + 3] Aromatic Ring Formation with Chan's Diene	692
20.5.13.1.8.2 Variation 2: Anionic [4 + 2] Aromatic Ring Formation by Phthalide Annulation	693
20.5.13.1.8.3 Variation 3: Anionic [5 + 1] Aromatic Ring Formation by Addition to Pyrylium Salts	694
20.5.13.1.9 Method 9: Construction of the Aromatic Ring by Radical Cyclizations of ß-Oxo Esters	695
20.5.13.1.10 Method 10: Construction of the Aromatic Ring by Cycloadditions	695
20.5.13.1.10.1 Variation 1: [4 + 2] Diels--Alder Cycloadditions and Aromatization	695
20.5.13.1.10.2 Variation 2: Transition-Metal-Catalyzed [2 + 2 + 2] Cyclotrimerization of Alkynes	697
20.5.13.1.11 Method 11: Construction of the Aromatic Ring by Electrocyclization and Elimination	697
20.5.13.1.12 Method 12: Oxidative Rearrangement of 2-(Hydroxyaryl) Acylhydrazones	698
20.5.13.1.13 Method 13: Lithiation and Alkylation of Benzoate Esters	698
20.5.14 Product Subclass 14: Alk-2-enoic Acid Esters	702
20.5.14.1 Synthesis of Product Subclass 14	702
20.5.14.1.1 Method 1: Alkoxycarbonylation of Alkenyl Organometallics	702
20.5.14.1.1.1 Variation 1: Metalation/Alkoxycarbonylation of Alkenyl Ethers, Sulfides, and Enecarbamates	702
20.5.14.1.1.2 Variation 2: Reductive Metalation/Alkoxycarbonylation of Haloalkenes	703
20.5.14.1.1.3 Variation 3: Reductive Alkoxycarbonylation of Alkynes	704
20.5.14.1.1.4 Variation 4: Zirconium-Catalyzed Carboalumination/Alkoxycarbonylation of Alkynes	705
20.5.14.1.1.5 Variation 5: Palladium-Catalyzed Carbonylation/Alkoxylation of Alkenyl Electrophiles	705
20.5.14.1.2 Method 2: Elimination Reactions	706
20.5.14.1.2.1 Variation 1: Oxidative Elimination of Hydrogen from Alkanoic Acid Esters	706
20.5.14.1.2.2 Variation 2: Palladium-Mediated Oxidation of Silyl Enol Ethers	707
20.5.14.1.2.3 Variation 3: Elimination from ß-Heteroatom-Substituted Alkanoic Acid Esters	708
20.5.14.1.2.4 Variation 4: Elimination from a-Heteroatom-Substituted Alkanoic Acid Esters	709
20.5.14.1.2.5 Variation 5: Pericyclic syn-Elimination from a-Acetoxy, a-Sulfinyl, and a-Seleninyl Alkanoic Acid Esters	710
20.5.14.1.2.6 Variation 6: Reductive Elimination of Vicinal Heteroatom Substituents	711
20.5.14.1.2.7 Variation 7: Conversion of a-Oxo Esters into 2-Alkoxy- and 2-Aminoalk-2-enoic Acid Esters	712
20.5.14.1.2.8 Variation 8: Conversion of ß-Oxo Esters into 3-Alkoxy- and 3-Aminoalk-2-enoic Acid Esters	713
20.5.14.1.3 Method 3: Aldol-Type Condensations	714
20.5.14.1.3.1 Variation 1: Knoevenagel and Doebner-Modified Knoevenagel Condensations	714
20.5.14.1.3.2 Variation 2: Stobbe Condensation	716
20.5.14.1.3.3 Variation 3: Carbonyl Homologation by Siloxyalkynes and Alkoxyalkynes	716
20.5.14.1.4 Method 4: Wittig and Related Alkenylations	717
20.5.14.1.4.1 Variation 1: Wittig Reaction	718
20.5.14.1.4.2 Variation 2: Horner--Wittig Reaction	719
20.5.14.1.4.3 Variation 3: Horner--Wadsworth--Emmons Reaction	719
20.5.14.1.4.4 Variation 4: The Peterson Alkenation	721
20.5.14.1.4.5 Variation 5: Alkenation of a-Oxo Esters	722
20.5.14.1.5 Method 5: Eschenmoser Sulfide Contraction	723
20.5.14.1.6 Method 6: Semihydrogenation of Alk-2-ynoic Acid Esters	723
20.5.14.1.7 Method 7: Phosphine-Catalyzed Internal Redox Isomerization of Alk-2-ynoic Acid Esters to Dienoic Acid Esters	725
20.5.14.1.8 Method 8: Conjugate Addition to Alk-2-ynoic Acid Esters	726
20.5.14.1.9 Method 9: Cycloadditions of Alk-2-ynoic Acid Esters	727
20.5.14.1.10 Method 10: a-Alkylation of Preformed Alk-2-enoic Acid Esters	729
20.5.14.1.11 Method 11: Conjugate Addition--Elimination of 3-Heterosubstituted Alk-2-enoic Acid Esters	730
20.5.14.1.12 Method 12: Transition-Metal-Catalyzed Cross Couplings of Alk-2-enoic Acid Esters	731
20.5.14.1.13 Method 13: Heck Reaction	733
20.5.14.1.14 Method 14: Alkene Metathesis	734
20.5.15 Product Subclass 15: 3-Oxo- and 3,3-Diheteroatom-Substituted Alkanoic Acid Esters	738
20.5.15.1 Synthesis of Product Subclass 15	738
20.5.15.1.1 3-Oxoalkanoic Acid Esters	738
20.5.15.1.1.1 Method 1: Oxidation of 3-Hydroxyalkanoic Acid Esters	738
20.5.15.1.1.2 Method 2: Addition of Methyl Ketones to Carbonyl Compounds	739
20.5.15.1.1.2.1 Variation 1: Using Carbonates	739
20.5.15.1.1.2.2 Variation 2: Using Cyanoformates	739
20.5.15.1.1.2.3 Variation 3: Using Chloroformates	740
20.5.15.1.1.3 Method 3: Addition of 2,2-Dimethyl-1,3-dioxane-4,6-dione to Acylating Agents	741
20.5.15.1.1.3.1 Variation 1: Using Acid Chlorides	741
20.5.15.1.1.3.2 Variation 2: Using Activated Carboxylic Acids	742
20.5.15.1.1.3.3 Variation 3: Using Imidates	743
20.5.15.1.1.4 Method 4: Addition of Nitroalkanes to Ethyl Glyoxalate	743
20.5.15.1.1.5 Method 5: Addition of the Enolates of Acetates to Carbonyl Compounds	744
20.5.15.1.1.5.1 Variation 1: Using Acid Chlorides	744
20.5.15.1.1.5.2 Variation 2: Using Mixed Anhydrides	745
20.5.15.1.1.5.3 Variation 3: Using 1-Alkanoylimidazoles	746
20.5.15.1.1.5.4 Variation 4: Using N-Methoxy-N-methylamides	746
20.5.15.1.1.5.5 Variation 5: Using a Lithium (Trimethylsilyl)acetate and a 1-Acylimidazole	747
20.5.15.1.1.6 Method 6: Addition of Acetates to Acid Chlorides (via a Titanium Enolate)	748
20.5.15.1.1.7 Method 7: Addition of Acetates to Carbonyl Compounds (via a Formal Zinc Enolate)	748
20.5.15.1.1.7.1 Variation 1: Using a Reformatsky Reagent and an Acid Chloride	748
20.5.15.1.1.7.2 Variation 2: Using a Reformatsky Reagent and a Nitrile	749
20.5.15.1.1.8 Method 8: Claisen Condensation of Acetates	750
20.5.15.1.1.9 Method 9: Rearrangement of (Alkanoylsulfanyl)acetates	750
20.5.15.1.1.10 Method 10: Addition of Ethyl Diazoacetate to Aldehydes	750
20.5.15.1.1.11 Method 11: Reduction of Ethyl 3-Oxo-2-(triphenylphosphoranylidene)alkanoates	751
20.5.15.1.1.12 Method 12: Elimination of a Heterocylic Substituent from a 3-Hetaryl-3-hydroxyalkanoate	752
20.5.15.1.1.12.1 Variation 1: Elimination of Pyrrole from 3-Hydroxy-3-(1H-pyrrol-1-yl)alkanoates	752
20.5.15.1.1.12.2 Variation 2: Deprotection of tert-Butyl 3-Hydroxy-3-(1-methyl-1H-imidazol-2-yl)nonanoate	752
20.5.15.1.1.13 Method 13: Pyrolysis of 3-Hydroxy-2-(phenylsulfinyl)alkanoic Acid Esters	753
20.5.15.1.1.14 Method 14: Acylation of 3-Oxoalkanoic Acid Esters	753
20.5.15.1.1.14.1 Variation 1: Acylation of Methyl Acetoacetate with Acid Chlorides	753
20.5.15.1.1.14.2 Variation 2: Acylation of 3-Oxoalkanoic Acid Esters with Nitriles	754
20.5.15.1.1.15 Method 15: Acylation of Malonates	755
20.5.15.1.1.15.1 Variation 1: Acylation of Dialkyl Malonates with Acid Chlorides	755
20.5.15.1.1.15.2 Variation 2: Acylation of Magnesium Methyl Malonate with 1-Acylimidazoles	756
20.5.15.1.1.15.3 Variation 3: Acylation of Ethyl Hydrogen Malonate	756
20.5.15.1.1.15.4 Variation 4: Acylation of Methyl Tetrahydro-2H-pyran-2-yl Malonate	757
20.5.15.1.1.16 Method 16: Oxidation of Methyl Alk-2-ynoates	757
20.5.15.1.1.17 Method 17: Oxidation of Alk-2-enoates	758
20.5.15.1.1.17.1 Variation 1: Wacker Oxidation	758
20.5.15.1.1.17.2 Variation 2: Epoxidation and Rearrangement of Alk-2-enoic Esters	759
20.5.15.1.1.18 Method 18: Acetoacetylation of Alcohols Using Diketene	759
20.5.15.1.1.19 Method 19: Addition of Diketene to Aldehydes or Acetals	760
20.5.15.1.1.19.1 Variation 1: From Aldehydes	760
20.5.15.1.1.19.2 Variation 2: From Acetals	761
20.5.15.1.1.20 Method 20: Transesterification of 1,3-Dioxin-4-ones	762
20.5.15.1.1.21 Method 21: Alkylation of 3-Oxoalkanoic Acid Esters	764
20.5.15.1.2 3,3-Difluoroalkanoic Acid Esters	765
20.5.15.1.2.1 Method 1: Fluorination of Ethyl 3-Oxoalkanoates	765
20.5.15.1.2.2 Method 2: Reaction of Fluorinated Alkenes and Trimethyl Orthoacetate	765
20.5.15.1.2.3 Method 3: Transesterification of 3,3-Difluoroalkanoic Acid Esters	766
20.5.15.1.3 3,3-Dioxyalkanoic Acid Esters	766
20.5.15.1.3.1 Method 1: Addition of a Silyl Ketene Acetal to 2-Ethoxy-2-methyl-1,3-dioxolane	766
20.5.15.1.3.2 Method 2: Addition of a Silyl Ketene Acetal to a 1,3-Dioxolan-2-ylium Cation	767
20.5.15.1.3.3 Method 3: Addition of Pyrocatechol to Alkyl Penta-2,3-dienoates	767
20.5.15.1.4 3-Oxy-3-sulfanylalkanoic Acid Esters	768
20.5.15.1.4.1 Method 1: Addition of 2-Sulfanylphenol to Alkyl Penta-2,3-dienoates	768
20.5.15.1.5 3-Amino-3-oxyalkanoic Acid Esters	768
20.5.15.1.5.1 Method 1: Addition of the Lithium Enolate of an Ester to 1-Alkanoyl-1H-pyrroles	768
20.5.15.1.6 3,3-Disulfanylalkanoic Acid Esters	769
20.5.15.1.6.1 Method 1: Addition of 4-Methylbenzene-1,2-dithiol to Methyl Penta-2,3-dienoate	769
20.5.15.1.7 3-Amino-3-sulfanylalkanoic Acid Esters	769
20.5.15.1.7.1 Method 1: Addition of 2-Aminoethanethiol to an Alk-2-ynoic Acid Ester	769
20.5.16 Product Subclass 16: 3-Heteroatom-Substituted Alkanoic Acid Esters	772
20.5.16.1 Synthesis of Product Subclass 16	772
20.5.16.1.1 Haloalkanoic Acid Esters	772
20.5.16.1.1.1 Method 1: C==C Addition Reactions	772
20.5.16.1.1.2 Method 2: Nucleophilic Substitutions	773
20.5.16.1.1.3 Method 3: Cycloaddition Reactions	774
20.5.16.1.1.4 Method 4: Ring Opening	776
20.5.16.1.2 Hydroxy- and Sulfanylalkanoic Acid Esters and Derivatives	777
20.5.16.1.2.1 Method 1: Addition to a,ß-Unsaturated Esters	777
20.5.16.1.2.1.1 Variation 1: Michael Addition	777
20.5.16.1.2.1.2 Variation 2: Oxidative Addition	778
20.5.16.1.2.2 Method 2: Nucleophilic Substitutions	780
20.5.16.1.2.3 Method 3: Cycloaddition Reactions	783
20.5.16.1.2.3.1 Variation 1: Cyclopropanation of Functionalized Alkenes	783
20.5.16.1.2.3.2 Variation 2: [2 + 2] Cycloaddition	784
20.5.16.1.2.3.3 Variation 3: Diels--Alder Reaction	786
20.5.16.1.2.4 Method 4: Ring Opening of Cyclic Precursors	788
20.5.16.1.2.4.1 Variation 1: Ring Opening of Lactones	788
20.5.16.1.2.4.2 Variation 2: Ring Opening of Epoxides	789
20.5.16.1.2.5 Method 5: Reduction of ß-Dicarbonyl Compounds	790
20.5.16.1.2.5.1 Variation 1: Selective Reductions of ß-Oxo Esters	790
20.5.16.1.2.5.2 Variation 2: Monoreduction of Malonates	792
20.5.16.1.2.6 Method 6: Oxidation Reactions	794
20.5.16.1.2.6.1 Variation 1: Oxidation of a Preexisting Alcohol or Aldehyde Function	794
20.5.16.1.2.6.2 Variation 2: “Ex-novo” Oxidative Insertion of the Ester Function	796
20.5.16.1.2.6.3 Variation 3: Oxidative Insertion of the Hydroxy Function	797
20.5.16.1.2.7 Method 7: Carboxylation Reactions	798
20.5.16.1.2.8 Methods 8: Miscellaneous Reactions	799
20.5.16.1.3 Amino- and Phosphorylalkanoic Esters and Derivatives	799
20.5.16.1.3.1 Method 1: Addition to a,ß-Unsaturated Esters	799
20.5.16.1.3.1.1 Variation 1: Michael Addition	799
20.5.16.1.3.1.2 Variation 2: Oxidative Addition	805
20.5.16.1.3.2 Method 2: Nucleophilic Substitutions	807
20.5.16.1.3.3 Method 3: Cycloaddition Reactions	809
20.5.16.1.3.3.1 Variation 1: Cyclopropanation of Functionalized Alkenes	809
20.5.16.1.3.3.2 Variation 2: [2 + 2] Cycloaddition	810
20.5.16.1.3.4 Method 4: Ring Opening of Cyclic Precursors	812
20.5.16.1.3.4.1 Variation 1: Ring Opening of Lactams	812
20.5.16.1.3.4.2 Variation 2: Ring Opening of Epoxides	813
20.5.16.1.3.4.3 Variation 3: Ring Opening of Isoxazolidines	814
20.6 Product Class 6: Lactones	818
20.6.1 Synthesis of Product Class 6	821
20.6.1.1 Method 1: Lactonization	821
20.6.1.1.1 Variation 1: Lactonization To Give Five-Membered Lactones	821
20.6.1.2 Method 2: Asymmetric Dihydroxylation Followed by Lactonization	823
20.6.1.2.1 Variation 1: Butyrolactones from 1,4-Unsaturated Esters	823
20.6.1.2.2 Variation 2: Butyrolactones from 1,3-Unsaturated Esters	826
20.6.1.2.3 Variation 3: Butyrolactones from Epoxides and C2 Building Blocks	828
20.6.1.2.4 Variation 4: Butyrolactones from the Addition of C3 Building Blocks to Carbonyl Compounds	835
20.6.1.3 Method 3: Metalation of Aromatic Carboxylic Acid Derivatives	841
20.6.1.3.1 Variation 1: Base-Induced Lactonization	844
20.6.1.3.2 Variation 2: Lactonization To Give Six-Membered Lactones	846
20.6.1.3.3 Variation 3: d-Lactones from the Opening of Epoxides with C3 Building Blocks	848
20.6.1.3.4 Variation 4: d-Lactones from the Addition of C4 Building Blocks to Carbonyl Compounds	850
20.6.1.3.5 Variation 5: Lactonization To Give Four-Membered Lactones	852
20.6.1.4 Method 4: Macrolactonization and Difficult Lactonizations	853
20.6.1.4.1 Variation 1: The Corey--Nicolaou Method	853
20.6.1.4.2 Variation 2: The Masamune Method	856
20.6.1.4.3 Variation 3: The Mukaiyama Method	856
20.6.1.4.4 Variation 4: The Steliou Method	857
20.6.1.4.5 Variation 5: The Yamaguchi Method	859
20.6.1.4.6 Variation 6: Using Other Benzoic Acid Anhydrides	862
20.6.1.4.7 Variation 7: The Keck Method	863
20.6.1.4.8 Variation 8: Cyclization of 9-Hydroxydecanoic Acid	865
20.6.1.4.9 Variation 9: The Trost Method	865
20.6.1.4.10 Variation 10: Other Routes	867
20.6.1.5 Method 5: Lactones by Cycloalkylating Reactions	867
20.6.1.6 Method 6: Mitsunobu Lactonization	872
20.6.1.7 Method 7: Lactonization of Unsaturated Carboxylic Acids	878
20.6.1.7.1 Variation 1: Proton-Catalyzed Lactonization	879
20.6.1.7.2 Variation 2: Halolactonization	879
20.6.1.7.3 Variation 3: (Phenylselanyl)- and (Phenylsulfanyl)lactonization	890
20.6.1.8 Method 8: Lactones by Intramolecular Epoxide Opening with Carboxy Functions	892
20.6.1.9 Method 9: Spiro Lactones by Oxidative Cyclization	893
20.6.1.10 Method 10: Lactones by Baeyer--Villiger Oxidation	895
20.6.1.10.1 Variation 1: Baeyer--Villiger Oxidation of Cyclobutanones	895
20.6.1.10.2 Variation 2: Baeyer--Villiger Oxidation of Monocyclic, Annulated, and Spirocyclic Ketones	899
20.6.1.10.3 Variation 3: Baeyer--Villiger Oxidation of Bi- and Polycyclic Ketones	906
20.6.1.10.4 Variation 4: Macrolactones by Baeyer--Villiger Oxidation	910
20.6.1.10.5 Variation 5: Enzymatic Baeyer--Villiger Reactions	911
20.6.1.10.6 Variation 6: Metal-Catalyzed Baeyer--Villiger Oxidation	913
20.6.1.11 Method 11: ß-Lactones by [2 + 2]-Cycloaddition Reactions	916
20.6.1.12 Method 12: Lactones from Heterocyclic Precursors	925
20.6.1.12.1 Variation 1: Reduction of Cyclic Anhydrides to Lactones	925
20.6.1.13 Method 13: Butenolides from Furans	928
20.6.1.13.1 Variation 1: Unsaturated d-Lactones from Glycals	931
20.6.1.14 Methods 14: Other Methods	933
20.7 Product Class 7: Peroxy Acids and Derivatives	950
20.7.1 Product Subclass 1: Peroxy Acids, Peroxy Acid Salts, and Peroxy Acid Esters	950
20.7.1.1 Synthesis of Product Subclass 1	950
20.7.1.1.1 Method 1: Synthesis of Phthaloyl Peroxide	950
20.7.1.2 Applications of Product Subclass 1 in Organic Synthesis	951
20.7.1.2.1 Method 1: Asymmetric Allylic Oxidation of Alkenes	951
20.7.1.2.2 Method 2: Diastereofacial Selective Epoxidation	955
20.7.1.2.3 Method 3: Hydrolysis of Peroxy Esters in the Presence of Bis(tributyltin) Oxide	957
20.7.2 Product Subclass 2: O-Acylhydroxylamines and Related Compounds	957
20.7.2.1 Synthesis of Product Subclass 2	957
20.7.2.1.1 Method 1: N-Aryl-O-benzoylhydroxylamines by Reaction of N-Arylhydroxylamines with Benzoyl Chloride	957
20.7.2.1.2 Method 2: N-Alkyl-O-benzoylhydroxylamines by Reduction of Oxime Benzoates	958
20.7.2.1.3 Method 3: O-Aroylhydroxylamines from Aroyl Cyanides or Aroyl Chlorides	959
20.7.2.1.4 Method 4: O-Acetyl-N-allyl-N-pent-4-enoylhydroxylamine from O-Acetyl-N-allylhydroxylamine	961
20.7.2.1.5 Method 5: Cysteine Protease Inhibitor	961
20.7.2.1.6 Method 6: Optically Active Isoxazolidin-5-ones from Nitrones	962
20.7.2.1.7 Method 7: 3-Phenylcyclobutanone O-Benzoyloxime from Hydroxylamine and Benzoyl Chloride	963
20.7.2.1.8 Method 8: Optically Pure Spiro-.4-sulfanes from Sulfides	963
20.7.2.1.8.1 Variation 1: Stereospecific Synthesis of Optically Active (Acylamino)(acyloxy)diarylspiro-.4-sulfanes	964
20.7.2.1.8.2 Variation 2: Bis(acyloxy)spiro-.4-sulfanes from Sulfoxides	965
20.7.2.1.9 Method 9: Trihalomethanesulfenyl Acetates and Trifluoroacetates from Sulfenyl Chlorides	965
20.7.2.1.10 Method 10: (R)-Acetyl 1,1'-Binaphthyl-2,2'-diyl Phosphite	966
20.7.2.1.11 Method 11: Carboxyalkyl a-Aminoalkylphosphonic Acid Monoesters from Spirophosphoranes	967
20.7.2.1.12 Method 12: A (Benzoyloxy)(benzyl)phenylphosphine--Tungsten Complex via Phospha-Wittig Reaction	968
20.7.2.1.12.1 Variation 1: Synthesis of 1,2-Oxaphosphole--Pentacarbonyltungsten Complexes	968
20.7.2.1.13 Method 13: Spiro-.4-selanes from Selenides	969
20.7.2.1.13.1 Variation 1: Acyloxy-.4-selanes from Carboxylic Acids by Chlorination	970
20.7.2.1.13.2 Variation 2: Trifluoroacetoxy-.4-selanes from Selenoxides	970
20.7.2.1.14 Method 14: A Phenylselanyl Ester in Roseophilin Synthesis	970
20.7.2.1.15 Method 15: Benzeneselenenyl Trifluoroacetate from Benzeneseleninic Anhydride and Diphenyl Diselenide	971
20.7.2.1.16 Method 16: Spiro-.4-tellane Synthesis Using the 2-exo-Hydroxy-10-bornyl Group as a Chiral Ligand	971
20.7.2.1.17 Method 17: Macrocyclic Multi-.4-tellanes by Reaction of a Telluronium Salt with Phthalate Salts	972
20.7.2.2 Applications of Product Subclass 2 in Organic Synthesis	973
20.7.2.2.1 Method 1: Synthesis of Adenosine Derivatives	973
20.7.2.2.2 Method 2: Conversion of Cyclobutanone O-Benzoyloximes into Nitriles	974
20.7.2.2.3 Method 3: Synthesis of Secondary Amines	974
20.7.2.2.4 Method 4: Synthesis of N-Hydroxy Peptides	975
20.7.2.2.5 Method 5: Synthesis of the N-tert-Butyl-N-(3,5-dinitrobenzoyl)nitroxyl Radical	975
20.7.2.2.6 Method 6: Addition of Trihalomethanesulfenyl Acetates to Alkenes	976
20.7.2.2.7 Method 7: Synthesis of Thioacetylated Lactosides	976
20.7.2.2.8 Method 8: Reaction of Cyclic Phosphites with ß-Dicarbonyl Compounds	977
20.7.2.2.9 Method 9: Applications of Benzeneselenenyl Trifluoroacetate	978
20.7.2.2.10 Method 10: One-Pot Method for Alkene Trifunctionalization	979
20.7.2.2.11 Method 11: Transformation of Allylsilanes into Allylamines via Phenyltellurinylation	981
20.7.2.2.12 Method 12: Cyclofunctionalization of Alkenyl Carbamates Using Benzenetellurinic Trifluoroacetate	982
20.7.2.2.13 Method 13: Diacetoxylation of Dienes by Acetoxytelluration Followed by Acetylation	982
20.7.3 Product Subclass 3: Acetyl Hypohalites	984
20.7.3.1 Synthesis of Product Subclass 3	984
20.7.3.1.1 Method 1: Synthesis of Acetyl Hypohalites	984
20.7.3.2 Applications of Product Subclass 3 in Organic Synthesis	985
20.7.3.2.1 Method 1: Iodocyclization Using Acetyl Hypoiodite	985
20.7.3.2.2 Method 2: Fluorination Using Acetyl Hypofluorite	986
20.7.3.2.2.1 Variation 1: Direct Fluorination of Peptides Containing Tyrosine	986
20.7.3.2.2.2 Variation 2: Fluorination of 1,3-Dicarbonyl Derivatives	986
20.7.3.2.2.3 Variation 3: Fluorination of Nitro Compounds	987
20.7.3.2.2.4 Variation 4: Synthesis of a-Fluorocarboxylates	988
20.7.3.2.2.5 Variation 5: Acetoxylation of Nitrogen Heterocycles	988
20.7.4 Product Subclass 4: Peroxy Esters of Sulfur, Nitrogen, and Phosphorus	989
20.7.4.1 Synthesis of Product Subclass 4	989
20.7.4.1.1 Method 1: Pentafluorosulfur Peroxy Esters from Acyl Fluorides and Pentafluoro-.6-sulfane Hydroperoxide	989
20.7.4.1.2 Method 2: 1-(Benzoylperoxy)-2,2,6,6-tetramethylpiperidine by Direct Reaction of Dibenzoyl Peroxide	990
20.7.4.1.3 Method 2: Trifluoroacetyl Peroxynitrate by Nitration of Trifluoroperacetic Acid	990
20.7.4.2 Applications of Product Subclass 4 in Organic Synthesis	991
20.7.4.2.1 Method 1: As Radical Initiators Used in the Bulk Polymerization of Styrene	991
20.8 Product Class 8: Thiocarboxylic S-Acids, Selenocarboxylic Se-Acids, Tellurocarboxylic Te-Acids, and Derivatives	994
20.8.1 Product Subclass 1: Thiocarboxylic S-Acids and Their Salts	994
20.8.1.1 Synthesis of Product Subclass 1	995
20.8.1.1.1 Method 1: Acylation of a Sulfur Source	995
20.8.1.1.2 Method 2: Direct Thiation of Carboxylic Acids	997
20.8.1.1.3 Methods 3: Miscellaneous Procedures	998
20.8.2 Product Subclass 2: Thioanhydrides (Diacyl Sulfides)	1000
20.8.2.1 Synthesis of Product Subclass 2	1001
20.8.2.1.1 Method 1: Reaction of an Acylating Agent with a Sulfide Source	1001
20.8.2.1.2 Method 2: Reaction of Thiocarboxylic Acids and an Acylating Agent	1004
20.8.2.1.3 Methods 3: Miscellaneous Procedures	1006
20.8.3 Product Subclass 3: Acyl Sulfones	1007
20.8.3.1 Synthesis of Product Subclass 3	1007
20.8.3.1.1 Method 1: Oxidation of Thiocarboxylic Acid S-Esters	1007
20.8.3.1.2 Methods 2: Miscellaneous Procedures	1008
20.8.4 Product Subclass 4: Thiocarboxylic Acid S-Esters	1008
20.8.4.1 Synthesis of Product Subclass 4	1009
20.8.4.1.1 Method 1: Synthesis from Thiocarboxylic Acids	1009
20.8.4.1.1.1 Variation 1: Alkylation of Thiocarboxylic Acids with Alkyl Halides or Related Compounds	1009
20.8.4.1.1.2 Variation 2: Addition Reactions	1013
20.8.4.1.1.3 Variation 3: Arylation of Thiocarboxylic Acids	1015
20.8.4.1.2 Method 2: Acylation of Thiols	1016
20.8.4.1.2.1 Variation 1: Acylation by Carboxylic Acid Halides	1016
20.8.4.1.2.2 Variation 2: Acylation by Acid Anhydrides	1019
20.8.4.1.2.3 Variation 3: Acylation by Carboxylic Acids	1021
20.8.4.1.2.4 Variation 4: Acylation by Carboxylic Acid Esters	1024
20.8.4.1.3 Method 3: Carbonylation Reactions	1027
20.8.4.1.4 Method 4: Synthesis by Rearrangement	1031
20.8.4.1.5 Method 5: Synthesis by Modification of the Acyl Group	1032
20.8.4.1.6 Method 6: Synthesis by Modification of the Sulfur Unit	1035
20.8.4.1.7 Methods 7: Miscellaneous Procedures	1036
20.8.5 Product Subclass 5: Acylsulfenyl Halides	1038
20.8.5.1 Synthesis of Product Subclass 5	1038
20.8.5.1.1 Method 1: Direct Halogenation of Thiocarboxylic S-Acids or Their Salts	1038
20.8.6 Product Subclass 6: Acylsulfenic Acids and Derivatives	1040
20.8.7 Product Subclass 7: Diacyl Disulfides	1042
20.8.7.1 Synthesis of Product Subclass 7	1042
20.8.7.1.1 Method 1: Oxidation of Thiocarboxylic S-Acids	1042
20.8.7.1.2 Method 2: Reaction of Acid Chlorides and a Disulfide Source	1043
20.8.7.1.3 Method 3: Reaction of Thiocarboxylic S-Acids and Electrophilic Acylsulfanyl Donors	1044
20.8.7.1.4 Methods 4: Miscellaneous Procedures	1045
20.8.8 Product Subclass 8: Acyl Disulfides (Acyl Dithioperoxides)	1046
20.8.8.1 Synthesis of Product Subclass 8	1046
20.8.8.1.1 Method 1: Synthesis from Thiocarboxylic S-Acids and Electrophilic Sulfur Species	1046
20.8.8.1.2 Method 2: Synthesis from Acylsulfenyl Chlorides and Sulfur Nucleophiles	1047
20.8.8.1.3 Methods 3: Miscellaneous Procedures	1048
20.8.9 Product Subclass 9: S-Acyl Selenothioperoxides and Tellurothioperoxides	1049
20.8.9.1 Synthesis of Product Subclass 9	1050
20.8.9.1.1 Method 1: Synthesis from a Thiocarboxylic S-Acid and an Electrophilic Selenium or Tellurium Fragment	1050
20.8.9.1.2 Method 2: Synthesis from Acylsulfenyl Halides and Chalcogen Nucleophiles	1051
20.8.9.1.3 Methods 3: Miscellaneous Procedures	1052
20.8.10 Product Subclass 10: Acyl Sulfenamides and Related Compounds	1052
20.8.10.1 Synthesis of Product Subclass 10	1053
20.8.10.1.1 Method 1: Synthesis from Thiocarboxylic S-Acids and Electrophilic Amine Sources	1053
20.8.11 Product Subclass 11: Selenocarboxylic Acid Se-Esters and Tellurocarboxylic Acid Te-Esters	1055
20.8.11.1 Synthesis of Product Subclass 11	1057
20.8.11.1.1 Method 1: Selenocarboxylic Acid Se-Esters and Tellurocarboxylic Acid Te-Esters by Alkylation of Chalcogenocarboxylic Acids	1057
20.8.11.1.2 Method 2: Synthesis from Carboxylic Acids	1059
20.8.11.1.3 Method 3: Synthesis from Activated Esters	1062
20.8.11.1.4 Method 4: Synthesis from Carboxylic Acid Esters	1065
20.8.11.1.5 Methods 5: Miscellaneous Procedures	1067
20.8.12 Product Subclass 12: Other Acylselenium and Acyltellurium Compounds	1069
20.8.12.1 Synthesis of Product Subclass 12	1070
20.8.12.1.1 Method 1: Synthesis of Selenocarboxylic Se-Acids and Tellurocarboxylic Te-Acids	1070
20.8.12.1.2 Method 2: Synthesis of Diacyl Selenides (Selenoanhydrides) and Diacyl Tellurides (Telluroanhydrides)	1071
20.8.12.1.3 Method 3: Synthesis of Acyl Diselenides, Acyl Ditellurides, and Mixed Chalcogen Derivatives	1071
20.8.12.1.4 Method 4: Synthesis of Diacyl Diselenides and Diacyl Ditellurides	1072
20.8.12.1.5 Method 5: Synthesis of Acylselenenyl Halides	1072
20.8.12.1.6 Method 6: Synthesis of Acylselenium(IV) and Acyltellurium(IV) Compounds	1073
Keyword Index	1088
Author Index	1138
Abbreviations	1198

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