Sulfur Chemistry (eBook)

Contents 6
Preface 8
Analysis of US FDA-Approved Drugs Containing Sulfur Atoms 10
Abstract 10
1 Introduction 11
2 Diversity of Sulfur-Containing Functional Groups in US FDA Drugs 11
2.1 Sulfonamides 11
2.2 ?-Lactams 18
2.3 Thioethers 21
2.4 Thiazoles 24
2.5 Thiophenes 26
2.6 Phenothiazines 28
2.7 Sulfoxides 29
2.8 C=S and P=S Structures 31
2.9 Thionucleotides 33
2.10 Sulfones 34
2.11 Sulfates 35
2.12 Macrocyclic Disulfides 37
2.13 Miscellaneous Acyclic Sulfur Functional Groups 38
2.14 Miscellaneous Cyclic Sulfur Functional Groups 39
3 US FDA Drugs Containing Multiple Sulfur Atoms 41
4 Presence of Sulfur Atoms in Combination Drugs 41
5 Conclusion 42
Acknowledgements 42
References 42
Sulfur-Containing Agrochemicals 44
Abstract 44
Introduction 45
Sulfonylureas 48
Sulfonylurea Herbicides 48
Sulfonylamino-Carbonyl-Triazolinones Herbicides 54
Sulfonamides 55
Sulfonamide Herbicides 55
Triazolopyrimidine Sulfonamide Herbicides 57
Sulfonamide Herbicide Safeners 58
Sulfonamide Fungicides 60
Sulfamide Fungicides 60
Sulfur-Containing Heterocyclics 61
Thiazole Fungicides 61
Thiazole Insecticides 63
Thiazole Herbicide Safener 65
Benzothiazole Herbicides 66
Thiazolidine Fungicides 67
Thiazolidine Insecticides 67
Thiophene Fungicides 68
Thiophene Nematicide 69
Thioureas 70
Sulfides, Sulfoxides, Sulfones 71
Methylthio-S-Triazine Herbicides 71
Sulfonyl-Isoxazoline Herbicides 72
Methyl Sulfone-Containing Herbicides 73
Sulfonyl--Triazole--Carboxamide Herbicides 76
Sulfone Nematicide 77
Sulfoximines 78
Conclusions 78
Acknowledgements 79
References 79
Thiophene-Based Organic Semiconductors 88
Abstract 88
Introduction 88
Thiophene 89
Thiophene-Based Small Molecules/Oligomers As Organic Semiconductors 91
Organic Photovoltaics 92
Organic Field-Effect Transistors 96
Organic Light-Emitting Diodes 98
Fused Thiophene-Based Small Molecules As Organic Semiconductors 101
Organic Photovoltaics 102
Organic Field-Effect Transistors 107
Organic Light-Emitting Diodes 110
Thiophene and Fused Thiophene-Based Polymers as Organic Semiconductors 113
Organic Photovoltaics 114
Organic Field-Effect Transistors 120
Organic Light-Emitting Diodes 122
Conclusions 126
References 127
Synthesis and Applications of Polymers Made by Inverse Vulcanization 133
Abstract 133
1 Synthesis of Polymers by Inverse Vulcanization 133
2 Applications of Polymers Prepared by Inverse Vulcanization 138
2.1 Cathode Materials for Li–S Batteries 138
2.2 Dynamic and Repairable Materials 140
2.3 Optics Applications 143
2.4 Metal Sorption 147
2.5 Oil Spill Remediation 151
2.6 Controlled-Release Fertilizers 151
3 Other Applications and Outlook 154
Acknowledgements 157
References 157
Engineered C–S Bond Construction 160
Abstract 160
1 Introduction 161
1.1 Importance of Thioethers 161
2 First-Row 3d Series Transition-Metal Catalysis 162
2.1 Fe, Mn, and Co-Catalyzed Reactions in C–S Bond Formation 162
2.2 Ni and Cu Catalysis in C–S Coupling Reactions 166
3 Second-Row 4d Series Transition-Metal Catalysis 179
3.1 Pd- and Ru-Catalyzed Reactions in C–S Bond Formation 179
3.2 Rh and Ag Catalysis in C–S Coupling Reactions 183
4 Third-Row 5d Series Transition-Metal Catalysis 184
4.1 La and Au Catalysis in C–S Bond Formation 184
5 Post-Transition Metal Catalysis 185
5.1 In and Bi Catalysis in C–S Cross-Coupling Reactions 185
6 Alternative Systems for C–S bond Formation by Using Different Sulfur-Containing Surrogates 186
6.1 Thiol as Sulfur-Containing Precursor 187
6.2 Disulfide and Sulfoxide as Sulfur-Containing Precursor 190
6.3 RSO2Na, Isothiocyanates, and Arenesulfonyl Hydrazine as Sulfur-Containing Precursor 196
7 Conclusions 200
Acknowledgements 201
References 201
C–S Bond Activation 205
Abstract 205
1 Introduction 205
2 Stoichiometric Reactions 206
2.1 Cleavage of C–S Bonds of Thiophene Analogues 206
2.2 Cleavage of Allylic C–S Bonds 208
2.3 Cleavage of Acyl C–S Bonds 209
2.4 Cleavage of Alkenyl and Aryl C–S Bonds 211
3 Catalytic Cross-Coupling Reactions 211
3.1 Cross-Coupling Reactions of Sulfides 212
3.1.1 Kumada–Tamao–Corriu-Type Coupling 212
3.1.2 Negishi-Type Coupling 213
3.1.3 Suzuki–Miyaura-Type Coupling 215
3.1.4 With Other Nucleophiles 216
3.2 Cross-Coupling Reactions of Thioesters 219
3.3 Cross-Coupling Reactions of Sulfonium Salts 221
3.4 Ring-Opening Transformation of Thiophenes 222
3.5 Cross-Coupling Reactions of Sulfoxides 225
3.6 Cross-Coupling Reaction of Sulfones 227
3.7 Cross-Coupling Reaction of Sulfonyl Chlorides 228
3.8 Cross-Coupling Reaction of Arylsulfinates 231
3.9 Cross-Coupling Reaction of Sulfonyl Hydrazides 232
4 Palladium-Catalyzed Desulfitative Addition of Arylsulfinates to Unsaturated Compounds 234
5 Transition Metal-Catalyzed Insertion of CO or Alkynes into C–S Bonds 235
5.1 Insertion of CO or Its Equivalent into C–S Bonds 235
5.2 Carbothiolation: Insertion of Alkynes into C–S Bonds 237
6 Conclusions 240
References 240
The Construction and Application of C=S Bonds 244
Abstract 244
1 General Aspects of Thiocarbonyl (C=S) Groups 244
2 Tautomerization 245
3 Generation and Synthesis of Thioaldehydes and Thioketones 247
4 Reactions of Thioaldehydes and Thioketones 254
4.1 Reactions with Nitrogen Nucleophiles 254
4.2 Reactions with Carbon Nucleophiles 254
4.3 Reactions with Carbon Electrophiles 259
4.4 Concerted Reactions 260
5 Conclusions 261
References 262
Thiophene Syntheses by Ring Forming Multicomponent Reactions 265
Abstract 265
1 Introduction 266
2 Ring-Forming Multicomponent Reactions 267
2.1 Outline 267
2.2 Sulfur Source Contributing 5 Atoms to the Thiophene Ring 267
2.3 Sulfur Source Contributing 4 Atoms to the Thiophene Ring 268
2.4 Sulfur Source Contributing 3 Atoms to the Thiophene Ring 268
2.4.1 Ketenimines as Key Intermediates 269
2.4.2 ?-Oxothiamides as Building Blocks 269
2.4.3 ?-Cyanothiamides 271
2.4.4 Dithioesters as Building Blocks 272
2.4.5 1,4-Dithiane-2,5-Diol 272
2.5 Sulfur Source Contributing 2 Atoms to the Thiophene Ring 272
2.5.1 Dithioester as a Building Block 272
2.5.2 Carbondisulfide 273
2.5.3 Thiocyanate 274
2.5.4 ?-Mercaptoester 277
2.5.5 Other Mercapto Derivatives 277
2.5.6 1,3-Thiazolidinedione 278
2.6 Sulfur Source Contributing 1 Atom to the Thiophene Ring 279
2.6.1 1,4-Phenylenedimethanethiol as a Sulfur Source 279
2.6.2 Sulfide as a Sulfur Source 279
2.6.3 Sulfur in a (2?+?2 + 1) Cycloaddition 281
2.6.4 The Gewald Reaction 282
3 Conclusions 282
Acknowledgements 282
References 282
Sulfur–Sulfur Bond Construction 288
Abstract 288
1 Introduction 288
2 The Construction of Symmetrical Disulfides 290
2.1 Oxidation of Thiol 292
2.1.1 O2 or Air as the Oxidant 292
2.1.2 Iodine, Bromine, and N-Bromo Derivatives 292
2.1.3 Hydrogen Peroxide (H2O2) as Oxidant 294
2.1.4 Metal Salt or Metal Oxide as Oxidant 294
2.1.5 High-Valent Sulfur Oxidant (DMSO, Sulfonyl Chloride, Peroxydisulfate) as Oxidant 295
2.1.6 Diethyl Azodicarboxylate (DEAD) and its Derivatives as Oxidant 295
2.1.7 Other Oxidants 296
2.1.8 Photo-catalyzed disulfide formation 296
2.2 Conversion from Sulfur Monochloride (S2Cl2) 299
2.3 Conversion from Sodium Disulfide (Na2S2) 301
2.4 Conversion from Elemental Sulfur 302
2.5 Reduction of Sulfonyl Halides 302
3 The Construction of Unsymmetrical Disulfides 303
3.1 Oxidation of Thiols 304
3.1.1 I2 as Oxidant 304
3.1.2 H2O2 as Oxidant 305
3.1.3 DDQ as Oxidant 306
3.1.4 Dimethyl Sulfoxide (DMSO) as Oxidant 307
3.1.5 DEAD and its Derivatives as Oxidant 307
3.2 Disulfane Exchange 309
3.2.1 Thiol Exchange with Symmetrical Disulfide 309
3.2.2 Rhodium-catalyzed Disulfane Exchange 310
3.3 Nucleophile Substitution Reaction 311
3.3.1 Benzotriazole (Bt) as the Leaving Group 311
3.3.2 Imides or N-Trifluoroacetyl as the Leaving Group 313
3.3.3 Sulfonyl and Sulfonates as the Leaving Group 314
3.3.4 Thiocarbonate and Thiophosphate as the Leaving Group 316
3.3.5 Chlorine as Leaving Group 317
3.4 The Oxidative Cross-coupling Reaction 319
3.5 The Opening of Thiiranes 320
3.6 The Comproportionation Between Two Different Inorganic Sulfur Salts 321
4 Conclusions 323
References 323
Sulfur Radicals and Their Application 328
Abstract 328
1 Thiyl (Sulfenyl) (RS·) and Related Sulfur Radicals 328
1.1 Thiol-ene and Thiol-yne 329
1.2 Other Reactions Forming C–S Bonds 334
1.2.1 Aryl C–S Bonds 334
1.2.2 Aliphatic C–S Bonds 336
1.2.3 Formation of S–S Bonds 338
1.2.4 Formation of C–C Bonds 338
1.2.5 Desulfurization 339
1.3 Photoredox Chemistry 339
1.4 Biochemistry 341
1.5 Thiocyanato Radical (·SCN) 342
1.6 Iminothiyl Radicals 342
1.7 Aminothiyl Radicals (R2N–S·) 343
2 Sulfinyl Radicals (RSO) 344
3 Sulfonyl Radicals (RSO2) 345
3.1 Addition to Alkenes and Alkynes 345
3.1.1 ?-Cyano Adducts 346
3.1.2 ?-Halo Adducts 346
3.1.3 Azide Adducts 346
3.1.4 Selenide Adducts 347
3.1.5 Trapping with Oxygen 347
3.1.6 Trapping Followed by Elimination or Substitution 348
3.1.7 Radical Oxidation 348
3.1.8 Trapping by Arene 348
3.1.9 Trapping by Alkene or Alkyne 349
3.1.10 Trapping by HAT 349
3.2 ?-Elimination of Sulfonyl Radicals 349
3.3 ?-Cleavage of Sulfonyl Radicals 350
4 Radical Ions 351
4.1 Two-Center Three-Electron Bonds 351
4.2 Reactions of Thioether Radical Cations 353
4.2.1 ?-C–H Bond Cleavage 353
4.2.2 ?-C–S Bond Cleavage 354
4.2.3 ? C–C Bond Cleavage 355
4.3 Oxidation 356
4.3.1 Photooxidation of Thioethers 356
4.3.2 Iron-Catalyzed Oxidation 356
4.4 Thioamide and Thiocarbamate Radical Cations 357
4.5 Disulfide Radical Cations 358
4.6 Sulfoxide Radical Cations 359
4.7 Disulfide Radical Anions 360
4.7.1 Alkyl and Aryl Disulfide Anion Radicals 360
4.7.2 Dithiocyanate Radical Anion 361
Acknowledgements 361
References 361
Glycosyl Sulfoxides in Glycosylation Reactions 370
Abstract 370
1 Introduction 371
2 Sulfinyl Group Located on Anomeric Position 372
2.1 Kahne Glycosylation 372
2.2 Crich cis-mannosylation 381
2.3 Oxathiane S-oxide Glycosylation 386
2.4 Mechanism Aspects 389
3 Sulfinyl Group Located at Remote Site of Anomeric Position 391
4 Conclusions 395
Acknowledgements 396
References 396
Chiral Sulfoxide Ligands in Asymmetric Catalysis 402
Abstract 402
1 Introduction 402
2 S-N Ligands 403
3 S-P Ligands 410
4 S–S Ligands 420
5 S-Olefin Ligands 425
6 S-O Ligands 427
7 Summary 428
Acknowledgements 428
References 428
Sulfur-Based Ylides in Transition-Metal-Catalysed Processes 431
Abstract 431
1 Introduction 432
2 Metal–Ylide Complexes 433
3 Non-Carbene-Based Transition Metal-Mediated Reactions of Sulfur Ylides 434
3.1 Sulfur Ylides as Single-Carbon Synthons in Formal (n?+?1) Cycloadditions 434
3.2 Transition Metals as ?-Acid Catalysts 439
3.3 Sulfoxonium Ylides in C–H Functionalisation Processes 445
3.4 Sulfonium Ylides as C–S Activation Precursors 447
3.5 Photocatalysis Involving Sulfonium Ylides 449
4 Sulfonium and Sulfoxonium Ylides as Metal-Carbene Precursors 451
4.1 Cyclopropanation Reactions 451
4.2 Insertion Reactions into X–H Bonds 453
4.3 Insertion Reactions into C–H Bonds 455
4.4 Miscellaneous Metal Carbenoid Reactions 457
5 Cascade Reactions Involving Transition Metal-Catalysed Ylide Formation 457
5.1 [2,3]-Rearrangement of Sulfonium Ylides 458
5.2 1,2-Migration of Sulfonium Ylides 468
5.3 Synthesis of Small Rings 470
5.3.1 Epoxidation 471
5.3.2 Aziridination 472
5.3.3 Cyclopropanation 472
5.4 In Situ Generation of Thiocarbonyl Ylides 472
6 Outlook 473
Acknowledgements 474
References 474