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Review
. 2024 Oct 9;124(19):11108-11186.
doi: 10.1021/acs.chemrev.4c00303. Epub 2024 Sep 13.

Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Akira Yoshimura  1 , Viktor V Zhdankin  2
Affiliations
Review

Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Akira Yoshimura et al. Chem Rev. .

Abstract

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. Hypervalent iodine reagents are commonly used in synthetically important halogenations, oxidations, aminations, heterocyclizations, and various oxidative functionalizations of organic substrates. Iodonium salts are important arylating reagents, while iodonium ylides and imides are excellent carbene and nitrene precursors. Various derivatives of benziodoxoles, such as azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, and alkenylbenziodoxoles have found wide application as group transfer reagents in the presence of transition metal catalysts, under metal-free conditions, or using photocatalysts under photoirradiation conditions. Development of hypervalent iodine catalytic systems and discovery of highly enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important recent achievement in the field of hypervalent iodine chemistry. Chemical transformations promoted by hypervalent iodine in many cases are unique and cannot be performed by using any other common, non-iodine-based reagent. This review covers literature published mainly in the last 7-8 years, between 2016 and 2024.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Preparation of (Difluoroiodo)arenes 2 with Ortho Substitution
Scheme 2
Scheme 2. Preparation of (Difluoroiodo)arenes 4 Using AgF2
Scheme 3
Scheme 3. Preparation of p-NO2C6H4IF(OTf) 6
Scheme 4
Scheme 4. Fluoro Sulfoximidations of Styrenes 9
Scheme 5
Scheme 5. Preparation of Phosphate Fluorides 12
Scheme 6
Scheme 6. Proposed Reaction Mechanism of Fluorination of Phosphine Oxide 11
Scheme 7
Scheme 7. Fluorination Reaction of Alkylsilanes 16
Scheme 8
Scheme 8. gem-Difluorination Reaction of Hydrazones 19
Scheme 9
Scheme 9. Preparation of α-(Difluoromethyl)styrenes 22
Scheme 10
Scheme 10. Synthesis of β-Difluorinated Alkylborons 25 from Styrenes 23
Scheme 11
Scheme 11. Proposed Mechanism of Formation of Products 25 from Styrenes 23
Scheme 12
Scheme 12. Preparation of Difluorinated Alkylidenecyclobutanes 31
Scheme 13
Scheme 13. Proposed Mechanism of Formation of Difluorinated Alkylidenecyclobutanes 31
Scheme 14
Scheme 14. Synthesis of μ-Fluorido-Diiron(III) Complex 38 and Monomeric Product 39
Scheme 15
Scheme 15. Fluorocarbonylation of Unactivated Alkenes 40
Scheme 16
Scheme 16. Reaction of β-Sulfidocarbonyl Compounds 43 with (Dichloroiodo)benzene 44
Scheme 17
Scheme 17. Preparation of Tetracoordinated Hypervalent Iodine Compound 46
Scheme 18
Scheme 18. gem-Dichlorination of Aromatic Isonitriles 47 Using 44
Scheme 19
Scheme 19. Proposed Mechanism of gem-Dichlorination Reaction of Aromatic Isonitriles 47
Scheme 20
Scheme 20. Reaction of Methyl o-Alkynylbenzoates 51 with Reagent 44
Scheme 21
Scheme 21. Proposed Mechanism of Chlorolactonization of Methyl o-Alkynylbenzoates 51
Scheme 22
Scheme 22. Oxidative Cyclization Reaction of Alkynone (Z)-o-Methyl Oximes 56
Scheme 23
Scheme 23. gem-Chlorosulfurization of p-Toluenesulfonyl Difluorodiazoethane 58
Scheme 24
Scheme 24. Preparation of 2-Amino-1,3-selenazoles 61
Scheme 25
Scheme 25. Preparation of Thiocyanated Isobenzofuranones 63
Scheme 26
Scheme 26. Proposed Mechanism of Formation of Thiocyanated Isobenzofuranones 63
Scheme 27
Scheme 27. Reaction of 4-Methylquinoline 68 and Alcohols 69 with Reagent 44 under Blue-LED
Scheme 28
Scheme 28. Preparation of Complex 72 using Reagent 44
Scheme 29
Scheme 29. Photolysis of Complex 72
Scheme 30
Scheme 30. Reaction of Gold Complexes 74 with Reagent 44
Scheme 31
Scheme 31. Preparation of Carbazole Compounds 78 from Anilines 77
Scheme 32
Scheme 32. Preparation of N-Acetoxyamides 80 from Aldoximes 79
Scheme 33
Scheme 33. Oxidative Rearrangement of Secondary Amines 81
Scheme 34
Scheme 34. Proposed Mechanism for the Formation of 82
Scheme 35
Scheme 35. DIB-Mediated Oxidative Cleavage Reaction of 5-Aminopyrazoles 85
Scheme 36
Scheme 36. DIB-Mediated Oxidative Ring-Expansion Reaction of 2-Aminobenzothiazoles 87
Scheme 37
Scheme 37. Denitrogenation of N-Arylsulfonylhydrazones 91 Using DIB 24
Scheme 38
Scheme 38. Cross-Coupling Reaction of N-Methoxyamide 93 and Benzotriazole 94
Scheme 39
Scheme 39. Preparation of Cycloheptatriene-Fused Lactam 97
Scheme 40
Scheme 40. Cycloaddition Reaction of Indoles 99
Scheme 41
Scheme 41. Proposed Mechanism for Cycloaddition Reaction of Compounds 98 and 99 Using Reagent 24
Scheme 42
Scheme 42. Preparation of Sulfonimidamides 105
Scheme 43
Scheme 43. Preparation of Sulfinimidate Esters 108
Scheme 44
Scheme 44. Allylic C–H Amination of 109
Scheme 45
Scheme 45. Proposed Mechanism of Product 112 Formation
Scheme 46
Scheme 46. Preparation of 5,5-Disubstituted Oxazolidine-2,4-dione 117
Scheme 47
Scheme 47. Proposed Mechanism for the Conversion of Compound 116 to Product 117
Scheme 48
Scheme 48. Sigmatropic Rearrangement Reactions Using DIB 24
Scheme 49
Scheme 49. Sigmatropic Rearrangement Reaction Using PIFA 136
Scheme 50
Scheme 50. Proposed Mechanism α-Arylation of Ketone 135
Scheme 51
Scheme 51. Preparation of Binaphthyl Compounds 142
Scheme 52
Scheme 52. α-Tosyloxylation of α,β-Unsaturated Compounds 144
Scheme 53
Scheme 53. Proposed Mechanism of α-Tosyloxylation Reaction of Compounds 144
Scheme 54
Scheme 54. Functionalization of 8-Aminoquinolinamides 148 Using (Diacyloxyiodo)benzene Reagents
Scheme 55
Scheme 55. Halocyclization of Sulfoximimes 153 Using DIB/KI Combination
Scheme 56
Scheme 56. Cyclizations of Amino Derivatives Using DIB 24 with an Additive
Scheme 57
Scheme 57. β C–H Amination of Imidate 165
Scheme 58
Scheme 58. Generation of Carbon Radicals 170 via HAT Reaction
Scheme 59
Scheme 59. Hydrodifluoromethylation of Alkenes 171
Scheme 60
Scheme 60. PIFA-Mediated Cascade Reaction of Phenolic Compound 174
Scheme 61
Scheme 61. PIFA- and I2-Meditated Cyclization of Amines 176
Scheme 62
Scheme 62. PIFA-Meditated Oxidative Dimerization of 2H-Indazole 178
Scheme 63
Scheme 63. Palladium-Catalyzed Cyclization of Alkenols 180
Scheme 64
Scheme 64. Palladium-Catalyzed Cyclizations of Benzylamide 183
Scheme 65
Scheme 65. Ring Rearrangement of 1,3-Azasilinyl-4-Epoxides 186
Scheme 66
Scheme 66. Copper-Catalyzed Coupling Reaction Between 188 and 189
Scheme 67
Scheme 67. Preparation of Gold(III) Complexes from 191 Using DIB 24
Scheme 68
Scheme 68. Photocatalyst-Mediated Decarboxylative Methylation of 194
Scheme 69
Scheme 69. Preparation of Oxo-Spiro Compounds 197 from 196 Using PhIO 17
Scheme 70
Scheme 70. Synthesis of Sulfonimidates 199 from Sulfinamides 198 and PhIO in the Presence of Alcohols
Scheme 71
Scheme 71. Preparation of Monofluorinated Five-Membered Ring-Fused Oxazolines
Scheme 72
Scheme 72. Synthesis of 10-Azacorroles 205
Scheme 73
Scheme 73. Lactonization Reaction of 206 with PhIO in Alcohol Solutions
Scheme 74
Scheme 74. Asymetric Epoxidation of Alkenes 208
Scheme 75
Scheme 75. Synthesis of 4-NO2C6H4I(NTf2)2212
Scheme 76
Scheme 76. Amination of Indole Compounds 213
Scheme 77
Scheme 77. Selective C–H Amidation of Indole 215
Scheme 78
Scheme 78. Preparation of NTs2-Substituted 2,5-Dihydrofuran 218
Scheme 79
Scheme 79. Proposed Reaction Mechanism for the Synthesis of 218 from 217
Scheme 80
Scheme 80. Preparation of (PhSO2)2N-Substituted Alkynes 222 from Alkynes 221
Scheme 81
Scheme 81. Oxidative Cyclization of N-Allylamides 223
Scheme 82
Scheme 82. Preparation of Ag(II) Complex 226
Scheme 83
Scheme 83. Synthesis of Aminocyclopropanes 228 from Allenes 227
Scheme 84
Scheme 84. Selective Benzylic C–H Amination of 229
Scheme 85
Scheme 85. Preparation of Hydrazinium Tosylate Salts 232
Scheme 86
Scheme 86. [2 + 2 + 1] Cycloaddition Reaction Using C6F5INTs
Scheme 87
Scheme 87. Photoinduced C–H Amination of Mesitylene 235 Using Reagent 236
Scheme 88
Scheme 88. Steps in the Formation of Tetrameric Molecule 240
Scheme 89
Scheme 89. Nitrooxylation of Cyclopropyl Trimethylsilyl Ether 242
Scheme 90
Scheme 90. Difunctionalization of 2H-Indazole 245
Scheme 91
Scheme 91. Synthesis of Carbazolones 249 from Exocyclic β-Enaminone 250
Scheme 92
Scheme 92. α-Arylation of Ketones 254 via Enolonium Species 252
Scheme 93
Scheme 93. Cyclization of Propargylic Alcohols 255 to Naphthyl(aryl)iodonium Triflates 256
Scheme 94
Scheme 94. Cyanotriflation of Alkynes 257
Scheme 95
Scheme 95. Preparation of p-NO2C6H4I(OTf)2259
Scheme 96
Scheme 96. Reaction of Triphenylmethane 260 with p-NO2C6H4I(OTf)2259
Scheme 97
Scheme 97. Trifluoromethylation-Cyclization of Isocyanides 263 with PhI(CF3)Cl 262
Scheme 98
Scheme 98. Synthesis of N-Trifluoromethyl Amidines 266 from Nitriles Using PhICF3Cl 262
Scheme 99
Scheme 99. Hydrotrifluoromethylation of Ynamides 268
Scheme 100
Scheme 100. Regio- and Stereoselective Perfluoropropylation of Alkyne 270
Scheme 101
Scheme 101. Diazirination of Carbohydrazides 273
Scheme 102
Scheme 102. α-Diazomethylation of Silyl Enol Ethers 277
Scheme 103
Scheme 103. ortho-Diazomethylation of Aromatic Tertiary Amines 277
Scheme 104
Scheme 104. [3 + 3] Annulation of Enaminones 282 Using Iodonium Ylide 281
Scheme 105
Scheme 105. Cyclization of Aromatic Tertiary Amines 284 Using Iodonium Ylide 285
Scheme 106
Scheme 106. Unactivated C(sp3)–H Bond Insertion Reaction of Pyridines 287
Scheme 107
Scheme 107. Copper-Catalyzed [2,3]-Sigmatropic Rearrangement
Scheme 108
Scheme 108. Radiofluorination of Iodonium Ylide 294
Scheme 109
Scheme 109. NHC-Catalyzed Synthesis of Ynones 298 from Alkynyliodonium Salts and Aldehydes
Scheme 110
Scheme 110. C2 Generation and Trapping Reaction in the Presence of 9,10-Dihydroanthracene 300
Scheme 111
Scheme 111. Reaction of Alkynyliodonium Salt 303 with N-(Acyloxy)sulfonamides 304
Scheme 112
Scheme 112. Synthesis of Indoles 308 from Arylhydroxylamines 306 and Vinyliodonium Salt 307
Scheme 113
Scheme 113. Aziridination of Amines 311 Using Vinyliodonium Salt 310
Scheme 114
Scheme 114. N-Alkylations of Anilines 314 Using Alkyliodonium Salt 313
Scheme 115
Scheme 115. Synthesis of Anilines 317 from Diaryiodonium Salts 316
Scheme 116
Scheme 116. 1,4-Double Cycloaddition of Diaryliodonium Triflate 318
Scheme 117
Scheme 117. Intramolecular Fluorination of Carbamates 321 Using Fluorobenziodoxole 322
Scheme 118
Scheme 118. Ring Expansion Fluorination of Cyclopropanes 324 Using Reagent 325
Scheme 119
Scheme 119. α-Functionalization of 2-Pyridyl Ketones 327
Scheme 120
Scheme 120. Dichlorination of Aromatic Allenes 329 Using Chlorobenziodoxole 330
Scheme 121
Scheme 121. Disulfonation of Terminal Alkynes 332
Scheme 122
Scheme 122. Ligand Exchange Reactions of Chlorobenziodazole 336
Scheme 123
Scheme 123. C–H Acyloxylation of Sulfides 339
Scheme 124
Scheme 124. Photocatalyst-Induced Intramolecular Cyclization of 342
Scheme 125
Scheme 125. Photocatalyst Mediated C–H Alkylation of 4-Chloroquinoline 346
Scheme 126
Scheme 126. Radical Reactions of Oxamic Acid 348 Using Acetoxybenziodoxole 344
Scheme 127
Scheme 127. Intramolecular Cyclization of Cyclic Alcohols 353
Scheme 128
Scheme 128. Cyanation of Alkyltrifluoroborates 355
Scheme 129
Scheme 129. Azido-Alkynylation of Alkenes 359
Scheme 130
Scheme 130. Dearomatic Azidation-Cyclization of Triptamines 362
Scheme 131
Scheme 131. Selective C–H Azidation of Indoles 365
Scheme 132
Scheme 132. Selective C–H Chlorination of Tertiary Alkyl Compounds 367
Scheme 133
Scheme 133. Bifunctionalization of Styrenes 369 Using 1-Sulfoximidoyl-1,2-benziodoxoles 370
Scheme 134
Scheme 134. Alkylamination of Styrenes 372
Scheme 135
Scheme 135. Preparation of Aminoketones 379 from Cyclic Alcohols 376 with Imides 378
Scheme 136
Scheme 136. C–H Insertion Amination Reaction of Thiophenes 381
Scheme 137
Scheme 137. Trifluoromethylation of Alcohols Using Cyclic Iodine(III) Reagent 384
Scheme 138
Scheme 138. Cyclotrifluoromethylation of Isocyanate Substrates Using 387
Scheme 139
Scheme 139. Bifunctionalization of Styrene 396
Scheme 140
Scheme 140. Bifunctionalization of Alkynes 403
Scheme 141
Scheme 141. C–H Trifluoromethylation of Pyrrolidine 405
Scheme 142
Scheme 142. C–H Perfluoroalkylation of Aromatic Compounds 407 and 409
Scheme 143
Scheme 143. Asymmetric α-Cyanation of β-Keto Esters 412
Scheme 144
Scheme 144. Decarboxylative Cyanation of Carboxylic Acids 415
Scheme 145
Scheme 145. Desilylative Cyanation of Amines 417
Scheme 146
Scheme 146. Synthesis of Dibenzotellurophene 420
Scheme 147
Scheme 147. Preparation of Polycyclic N-Heteroarenes 422
Scheme 148
Scheme 148. Palladium-Catalyzed Enantioselective Double Carbonylation
Scheme 149
Scheme 149. meta-Selective O-Arylation of Cyclic Iodonium Salt 419
Scheme 150
Scheme 150. Alkynylcarbonylation of Alkenes 428
Scheme 151
Scheme 151. Synthesis of Propargylic Esters 433 from Diazo Compounds 431
Scheme 152
Scheme 152. Preparation of Diynamides 436 from Amines 435 Using Reagent 434
Scheme 153
Scheme 153. Synthesis of Alkenylbenziodoxoles 439 from Alkynylbenziodoxoles 437
Scheme 154
Scheme 154. Alkenylation of Thiols 441 Using Alkenylbenziodoxoles 440
Scheme 155
Scheme 155. Preparation of Pseudocyclic Alkenyliodonium Triflates 445
Scheme 156
Scheme 156. Synthesis of Pseudocyclic Iodine(III) Compounds 447
Scheme 157
Scheme 157. Synthesis of Pseudocyclic Iodine(III) Compound 449 with 1H-Pyrazole Rings
Scheme 158
Scheme 158. Preparation of Cyclopropenium Salts 452 from Alkynes 450
Scheme 159
Scheme 159. Synthesis of Arylsulfonium Triflates 455 from Sulfides 454
Scheme 160
Scheme 160. Catalytic Difluorination of Enynes 456
Scheme 161
Scheme 161. Cycloisomerization-Arylation of N-Propargyl Amides 458
Scheme 162
Scheme 162. Decarboxylative Amination of Carboxylic Acids 461
Scheme 163
Scheme 163. Hypervalent Iodine-Mediated Intramolecular Cyclization of 463
Scheme 164
Scheme 164. Catalytic Intramolecular Cyclofluorination of Benzamides 465 and 467
Scheme 165
Scheme 165. Catalytic α-Tosyloxylation of Ketones 469
Scheme 166
Scheme 166. α-Amidation of 1,3-Dicarbonyl Compounds 471
Scheme 167
Scheme 167. Electrocatalytic Diacetoxylation of Alkenes 473
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References

    1. Zhdankin V. V.Hypervalent Iodine Chemistry: Preparation, Structure and Synthetic Application of Polyvalent Iodine Compounds; John Wiley & Sons Ltd: Chichester (UK), 2014.
    1. Wirth T.Hypervalent Iodine Chemistry: Modern Developments in Organic Synthesis. Top. Curr. Chem. 373; Springer, 2016.
    1. Olofsson B.; Marek I.; Rappoport Z.. Patai’s Chemistry of Functional Groups: The Chemistry of Hypervalent Halogen Compounds; Wiley: Chichester, UK, 2019.
    1. Ishihara K.; Muñiz K.. Iodine Catalysis in Organic Synthesis; Wiley-VCH: Weinheim, Germany, 2022.
    1. Simonet-Davin R.; Waser J. Azidation with Hypervalent Iodine Reagents. Synthesis 2023, 55, 1652–1661. 10.1055/a-1966-4974. - DOI

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