Viktor V Zhdankin Hypervalent Iodine Chemistry Preparation, Structure and Synthetic Applications of Polyvalent Iodine Compounds Hypervalent Iodine Chemistry Hypervalent Iodine Chemistry Preparation, Structure and Synthetic Applications of Polyvalent Iodine Compounds Viktor V Zhdankin Department of Chemistry and Biochemistry University of Minnesota Duluth, Minnesota, USA This edition first published 2014 © 2014 John Wiley & Sons, Ltd Registered office John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988 All rights reserved No part of this publication may be reproduced, stored in a retrieval 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ISBN: 9781118341032 Typeset in 10/12pt Times by Aptara Inc., New Delhi, India Contents Preface ix Introduction and General Overview of Polyvalent Iodine Compounds 1.1 Introduction 1.2 Classification and Nomenclature of Polyvalent Iodine Compounds 1.3 Hypervalent Bonding 1.4 General Structural Features 1.4.1 Experimental Structural Studies 1.4.2 Computational Studies 1.5 General Principles of Reactivity 1.5.1 Ligand Exchange and Reductive Elimination 1.5.2 Radical Reactions 1.5.3 Single-Electron Transfer (SET) Reactions References 1 11 12 13 14 15 15 Preparation, Structure and Properties of Polyvalent Iodine Compounds 2.1 Iodine(III) Compounds 2.1.1 Inorganic Iodine(III) Derivatives 2.1.2 Organoiodine(III) Fluorides 2.1.3 Organoiodine(III) Chlorides 2.1.4 Organo-Iodosyl Compounds 2.1.5 Organoiodine(III) Carboxylates 2.1.6 [Hydroxy(Organosulfonyloxy)Iodo]Arenes 2.1.7 Organoiodine(III) Derivatives of Strong Acids 2.1.8 Iodine(III) Heterocycles 2.1.9 Iodonium Salts 2.1.10 Iodonium Ylides 2.1.11 Iodine(III) Species with Three Carbon Ligands 2.1.12 Iodine(III) Species with I–N Bonds 2.2 Iodine(V) Compounds 2.2.1 Inorganic Iodine(V) Derivatives 2.2.2 Noncyclic and Pseudocyclic Iodylarenes 2.2.3 Iodine(V) Heterocycles 2.2.4 Organoiodine(V) Fluorides 2.3 Iodine(VII) Compounds References 21 21 21 23 27 31 35 43 48 50 76 99 107 107 114 114 115 120 126 127 128 vi Contents Hypervalent Iodine Reagents in Organic Synthesis 3.1 Reactions of Iodine(III) Compounds 3.1.1 Fluorinations 3.1.2 Chlorinations 3.1.3 Brominations 3.1.4 Iodinations 3.1.5 Oxidation of Alcohols 3.1.6 Oxidative Functionalization of Carbonyl Compounds 3.1.7 Oxidative Functionalization of Silyl Enol Ethers 3.1.8 Oxidation of Alkenes and Alkynes 3.1.9 Oxidations at the Benzylic or Allylic Position 3.1.10 Oxidative Functionalization of Aromatic Compounds 3.1.11 Oxidative Dearomatization of Phenols and Related Substrates 3.1.12 Oxidative Coupling of Aromatic Substrates 3.1.13 Oxidative Cationic Cyclizations, Rearrangements and Fragmentations 3.1.14 Oxidations at Nitrogen, Sulfur and other Heteroatoms 3.1.15 Azidations 3.1.16 Aminations 3.1.17 Thiocyanations and Arylselenations 3.1.18 Radical Fragmentations, Rearrangements and Cyclizations 3.1.19 Reactions via Alkyliodine(III) Intermediates 3.1.20 Transition Metal Catalyzed Oxidations 3.1.21 Transition Metal Catalyzed Aziridinations and Amidations 3.1.22 Reactions of Iodonium Salts and C-Substituted Benziodoxoles 3.1.23 Reactions of Iodonium Ylides 3.2 Synthetic Applications of Iodine(V) Compounds 3.2.1 Noncyclic and Pseudocyclic Iodylarenes 3.2.2 2-Iodoxybenzoic Acid (IBX) 3.2.3 Dess–Martin Periodinane (DMP) 3.2.4 Inorganic Iodine(V) Reagents 3.3 Synthetic Applications of Iodine(VII) Compounds References 145 145 146 152 158 160 164 168 171 173 181 182 183 196 201 216 222 230 232 236 248 250 253 260 278 282 283 288 296 302 303 307 Hypervalent Iodine Catalysis 4.1 Catalytic Cycles Based on Iodine(III) Species 4.1.1 Oxidative ␣-Functionalization of Carbonyl Compounds 4.1.2 Oxidative Functionalization of Alkenes and Alkynes 4.1.3 Oxidative Bromination of Aromatic Compounds 4.1.4 Oxidative Amination of Aromatic Compounds 4.1.5 Oxidation of Phenolic Substrates to Quinones and Quinols 4.1.6 Oxidative Spirocyclization of Aromatic Substrates 4.1.7 Carbon–Carbon Bond-Forming Reactions 4.1.8 Hofmann Rearrangement of Carboxamides 4.1.9 Oxidation of Anilines 4.2 Catalytic Cycles Based on Iodine(V) Species 4.3 Tandem Catalytic Systems Involving Hypervalent Iodine and other Co-catalysts 4.4 Catalytic Cycles Involving Iodide Anion or Elemental Iodine as Pre-catalysts References 337 337 338 342 346 347 349 350 354 355 357 358 364 368 377 Contents vii Recyclable Hypervalent Iodine Reagents 5.1 Polymer-Supported Iodine(III) Reagents 5.2 Polymer-Supported Iodine(V) Reagents 5.3 Recyclable Nonpolymeric Hypervalent Iodine(III) Reagents 5.3.1 Recyclable Iodine(III) Reagents with Insoluble Reduced Form 5.3.2 Recovery of the Reduced Form of a Hypervalent Iodine Reagent Using Ion-Exchange Resins 5.3.3 Ionic-Liquid-Supported Recyclable Hypervalent Iodine(III) Reagents 5.3.4 Magnetic Nanoparticle-Supported Recyclable Hypervalent Iodine(III) Reagent 5.3.5 Fluorous Recyclable Hypervalent Iodine(III) Reagents 5.4 Recyclable Nonpolymeric Hypervalent Iodine(V) Reagents 5.5 Recyclable Iodine Catalytic Systems References 381 381 389 391 393 397 400 401 402 405 406 409 Reactions of Hypervalent Iodine Reagents in Green Solvents and under Solvent-Free Conditions 6.1 Reactions of Hypervalent Iodine Reagents in Water 6.2 Reactions of Hypervalent Iodine Reagents in Recyclable Organic Solvents 6.3 Reactions of Hypervalent Iodine Reagents under Solvent-Free Conditions References 413 413 418 420 422 Practical Applications of Polyvalent Iodine Compounds 7.1 Applications of Inorganic Polyvalent Iodine Derivatives 7.2 Applications of Hypervalent Iodine(III) Compounds as Polymerization Initiators 7.3 Application of Iodonium Salts for Fluoridation in Positron Emission Tomography (PET) 7.4 Biological Activity of Polyvalent Iodine Compounds References 425 425 426 431 440 443 Index 449 454 Index Catalytic cycle for ␣-acetoxylation of ketones, 338, 339 for Hofmann rearrangement, 356, 357 involving iodine(V) as active species, 360 for metalloporphyrin-mediated oxygenations, 366 for oxidative bromination, 346, 347 Cation–radical intermediates, 15 in oxidation of phenol ethers, 197 Cationic polymerization, 427 C–C bond formation, hypervalent iodine-catalyzed, 354 C–C coupling reactions, Bu4 NI-catalyzed, 374, 375 (+)-Cephalostatin, synthesis, 298 Chalcones, rearrangement with [bis(trifluoroacetoxy)iodo]benzene, 210 C–H bond oxidation, using sodium 2-iodobenzenesulfonate as pre-catalyst and Oxone, 363, 364 Chiral (diacetoxyiodo)binaphthyl, degenerate isomerization, 10 Chlorinations, with (dichloroiodo)arenes, 152–158 of alkenes, 153 of aromatic compounds enantioselective dichlorination, 154, 155 1-Chloro-1,2-benziodoxol-3-(1H)-one preparation, 51 X-ray structure, 51, 52 as recyclable reagent for TEMPO-catalyzed oxidations, 393, 394 1-Chloro-4-fluoro-1H-1␭3 -benzo[d][1, 2,3]iodoxoborol-3-ol, 65 Chroman derivatives, synthesis by alkoxy radical fragmentation, 241 C–N coupling reactions, hypoiodite-catalyzed, 371–373 C-Nucleosides, preparation, 237 COX-2 inhibitors, [18 F]-labeled, 434 CP-molecules, synthesis, 299 Cross-coupling reactions, of alkenyliodonium salts, 269, 270 Cubyl ammonium salt, synthesis, by Hofmann rearrangement, 215 Cyanation, by cyanobenziodoxole, 278 Cyanobenziodoxole preparation and X-ray structure, 57 as reagent for cyanation, 277, 278 Cyanoiodonium salts, 94–96 Cyclic ethers, five- to seven-membered, synthesis by ring-enlargement, 207 Cyclizations, hypervalent iodine-catalyzed, 344, 348 Cycloalkanols, oxidation to enones, iodine(V) catalyzed, 363 Cycloetherification, hypoiodite-catalyzed, 370 Cyclohexadienimines, 2-alkynyl, by oxidative dearomatization of o-alkynylanilines, 196 Cyclohexa-2,4-dienones, 6,6-disubstituted as dienes in Diels–Alder cycloaddition, 194, 195 by oxidative dearomatization, 194 reaction with external dienophiles, 195 in synthesis of bacchopetiolone carbocyclic core, 195 Cyclohexadienones, 3,3-disubstituted, synthesis, by oxidative dearomatization, 184 Cyclohexadienyl(phenyl)iodonium salts, preparation, by Diels–Alder cycloadditions of alkynyliodonium salts, 87, 88 1-Cyclohexenyl(phenyl)iodonium salts cyclohexyne generation, 268 reactions with bases, 267, 268 (–)-Decarbamoyloxysaxitoxin, synthesis, 291 Decarboxylation, oxidative, with PhI(OAc)2 –iodine system, 239 1,2-Dehydrocarborane, 266 Deiodination, oxidative, of alkyliodides, 249 (±)-Deoxypreussomerin A, synthesis, 298 15-Deoxyripostatin A, synthesis, 299 Dess–Martin periodinane (DMP), 5, 124–126 dehydration of primary alcohols, 299 generation of acyl nitroso compounds, 300 glycol C–C bond cleavage, 298 oxidation of alcohols to carbonyl compounds, 296–299 oxidation of 1,2-diols, 298 oxidation of 2-hydroxyporphyrins and 2-aminoporphyrins, 300 oxidation of 4-substituted anilides to p-quinones, 301 oxidations in ionic liquids, 419 oxidative allylation of Morita–Baylis–Hillman adducts, 299 oxidative cleavage of oximes, 300 oxidative cyclization of anilides, 299, 301 preparation, 124, 125 properties, 125 as reagent, 282, 283, 296–302 synthesis of 2-substituted benzothiazoles, 302 ␣-tosyloxylation of ketones, 299 X-ray structure, 125, 126 (Diacetoxyiodo)arenes fluorous, 404 heteroaromatic derivatives, 37 ion-supported, 400, 401 optically active, preparation 36, 37 (Diacetoxyiodo)benzene abbreviations, 35 common names and abbreviations, 4, Index discovery, ligand exchange with methacrylic acid, 431 mechanism of palladium-catalyzed reactions, 252 oxidation of phenols, 184, 185, 192 oxidations of alcohols, in the presence of TEMPO, 414, 415 phenylsulfonate-tagged recyclable reagent, 399 preparation, by oxidation of PhI, 36, 37 reactions in water, 417 as reagent for Hofmann rearrangement, 213, 214 as terminal oxidant in transition metal-catalyzed oxidations, 252 tetraarylphosphonium (TAP)-supported, 401 X-ray structure, 41 1-(Diacetoxyiodo)-2-nitrobenzene, X-ray structure, 43 (Diacyloxyiodo)arenes antibacterial activity, 439 decarboxylative fragmentation, 238 Diacetoxylation of alkenes, hypervalent iodine-catalyzed, 342 Diacetoxylations, of alkenes by PhI(OAc)2 /BF3 ·OEt2 , syn and anti, 178 Diaminopimelic acid analogues, preparation, 238 2,3-Diarylbenzo[b]furans, synthesis, 206 Diaryl ethers, synthesis, 260–262 Diaryliodonium butyltriphenylborate salts, as photoinitiators, 430 Diaryliodonium chlorides, preparation using (E)-chlorovinyliodine(III) dichloride, 81 Diaryliodonium fluorides, ab initio computational studies of the extrusion reactions, 12 Diaryliodonium halides, X-ray structures, 84 Diaryliodonium salts activity against oral and dental anaerobes, 439 antifungal activity, 439 benzyne precursors, 266, 267 biocidal and antimicrobial activity, 439, 440 history, mechanism of photolysis, 427, 428 mechanism of reactions with nucleophiles, 264, 265 mechanism of solvolysis, 265 photoinitiators for cationic photopolymerizations, 426–431 polymer-supported, 388 PQQ inhibitors, 443 preparation, 76–81 reactions, 260–267 reagents for introduction of fluorine-18, 432 transition metal mediated cross-coupling reactions, 265, 266 455 Diaryliodonium tetrafluoroborates preparation, 80 X-ray structures, 84 Diaryliodonium tosylates, preparation from [hydroxy(tosyloxy)iodo]arenes and arylboronic acids, 78 from [hydroxy(tosyloxy)iodo]arenes and aryltributylstannanes, 78 from [hydroxy(tosyloxy)iodo]arenes and aryltrimethylsilanes, 78 Diaryliodonium triflates, preparation from (diacetoxyiodo)arenes and arenes, 78 from (diacetoxyiodo)arenes and arylboronic acids, 78 by one-pot reaction from iodine, arenes and mCPBA, 79 by one-pot reaction from iodoarenes, 78, 79 Dibenziodoles, 5-aryl-5H, 107 Dibenziodolium salts, preparation and X-ray structure, 74, 75 Dibenzo[a,c]phenanthridines, synthesis, 203 Dibenzoheterocyclic compounds, synthesis, by oxidation of phenol ethers, 198 (Dichloroiodo)arenes, 4, fluorous, 404 preparation, by ligand exchange, 29, 30 X-ray crystal structure, 30 (Dichloroiodo)benzene adduct with tetraphenylphosphonium chloride, 30 chlorination of aminoacetophenone, 155 chlorination of fullerene, 156 chlorination of ketones, 153 chlorination of monoterpenes, 153 chlorination of norbornene, 153, 154 chlorination and oxidation of transition metal complexes, 157, 158 chlorination of 3-substituted sydnones, 156 chlorination at sulfur, phosphorus, selenium, arsenic, antimony, 157 chlorination of 5,10,15-trisubstituted porphyrins, 155, 156 discovery, electrophilic reactivity of PhICl2 , 154 generation in situ, 157 mechanism of chlorinations, 152, 153 preparation, 27, 28, 30 as reagent for chlorinations, 152 X-ray crystal structure, 30 3-(Dichloroiodo)benzoic acid preparation, 28 as recyclable reagent, 393 as a stoichiometric oxidant, 393, 394 456 Index (Dichloroiodo)methylsulfones, ArSO2 CH2 ICl2 , preparation, 29 (Dichloroiodo)toluene, as reagent for catalytic asymmetric chlorinations, 153 (Dicyanoiodo)arenes, ArI(CN)2 , 107 (Dicyanoiodo)benzene, preparation and properties, 107 (Dicyano)iodonium triflate, preparation and properties, 94 (Difluoroiodo)arenes, electrochemical generation, 146 preparation, by electrochemical fluorination, 25, 26 X-ray crystal structure, 26, 27 (Difluoroiodo)benzene, preparation from PhI(OAc)2 and anhydrous tetrabutylammonium fluoride, 26 (Difluoroiodo)toluene, as fluorinating reagent, 146–152 electrochemical generation, 146 fluorination of cyclic ethers, 149 fluorination of thio- and seleno-glycosides, 147 fluorinative ring-expansion, 149 reaction with alkynes, 150 reaction with terminal alkenes, 150 10,11-Dihydrodibenz[b,f]iodeponium salt, 74, 75 2,3-Dihydrofuran derivatives, synthesis, 205 2,5-Dihydrofurans, synthesis from 3-alkoxy-1-alkynyl-(phenyl)iodonium triflates and sodium benzenesulfinate, 272 1,3-Dihydro-1-hydroxy-3-methyl-1,2,3benziodoxaphosphole 2-oxide, 69 5,6-Dihydroimidazo[2,1-b]thiazoles, 3-substituted, synthesis from alkynyliodonium salts, 271 Dihydrooxazole derivatives, synthesis, 206 Dihydropyran, oxidation with iodosylbenzene in water, 413, 414 2,2’-Diiodo-4,4’,6,6’-tetramethylbiphenyl, as catalyst, 347, 348, 353 5,5-Dimethyl-1,3-cyclohexanedione phenyliodonium ylide as carbenoid precursor, 278–280 ortho-alkoxy substituted, 280 in the synthesis of five-membered heterocycles, 279, 280 Dimethyldioxirane (DMDO) reaction with iodoarenes, 32 reaction with iodocyclohexane, 32 reaction with iodomethane, 32 Diphenyleneiodonium (DPI), 74 See also dibenziodolium Diphenyleneiodonium chloride (DPI) as a hypoglycaemic agent, 442 physiological effects, 442 Diphenyliodonium-2-carboxylate, see 1-phenyl-1,2-benziodoxole-3(1H)-one 2,3-Diphenylquinoxaline-1-oxide, synthesis, 206 Diselenides oxidation to selenosulfonates, 219, 220 oxidation to trifluoromethaneselenosulfonates, 220 Disproportionation, of iodine(III) species, RuCl3 -catalyzed, 367, 368 Ditellurides, oxidation to arenetellurinic mixed anhydrides, 219, 220 Diynyl(phenyl)iodonium triflates, 92 DOPA, synthesis, 296 (E)-chlorovinyliodine(III) dichloride, preparation and properties, 30 Elemental iodine, as pre-catalyst, 375–377 Enantioselective oxidative spirocyclization, with chiral iodoarenes as catalysts, 353 Enantioselective reactions, catalyzed by chiral iodoarenes, 338, 341, 342, 353, 354 Ent-hyperforin, synthesis, 298 (–)-Epibatidine, synthesis, 262 (±)-Epimaritidine, synthesis, 385 Epoxidation of alkenes, transition metal-catalyzed, 251 of electron-deficient alkenes, 179 enantioselective, catalyzed by chiral transition metal complexes, 251 organocatalytic, asymmetric, 179 of steroids, by PhIO2 /VO(acac)2 , 286 Epoxides, cleavage, with periodic acid, 303, 304 Epoxyquinomycin B, synthesis, 301 Erythromycin B, synthesis, 298 Ethynylbenziodoxolones, as acetylene transfer reagents, 273, 274 Eudistomin U, synthesis, 296 Farglitazar, fluorine-18 labeled, 437 Favorskii rearrangement, of steroidal substrates, 209 FD-891 16-membered macrolide, synthesis, 298 [18 F]DAA1106, PET ligand, synthesis, 437 [18 F]-fluoridation, with diaryliodonium salts with heteroaromatic iodonium salts, 435, 436 mechanistic and structural studies, 439 microreactor for fluoridation, 440 in the presence of radical scavengers, 434, 435 regioselectivity, 432–434 [18 F]-fluoride, cyclotron production, 432 [18 F]-fluoroarenes azido- or azidomethyl-substituted, 438 meta-substituted, 438 Index 3-[18 F]-fluorobenzaldehyde, 439 4-[18 F]-fluoroiodobenzene, 434 Five–membered iodine heterocycles, benziodoxoles and benziodazoles, 4, [18 F]-labeled radiotracers, 432, 434, 435 18 F-labeling, of the aromatic ring, 432 Fluorinations, with (difluoroiodo)arenes, see also [18 F]-fluoridation of alkenes, 149, 150 of dithioketals, 147 of ␤-ketoesters and ␤-dicarbonyl compounds, 146 mechanism of fluorination of ␣-phenylthio esters, 147, 148 of N-protected anilines, 152 of organosulfur compounds, 146, 147 of steroidal dienes, 150 of terminal alkynes, 150 Fluoroalkyl(aryl)iodonium salts, as electrophilic fluoroalkylating reagents, 275, 276 Fluoroalkylation of amino acids and peptides, 275 with fluoroalkyliodonium salts, 275, 276 Fluoroalkyliododichlorides, X-ray crystal structures, 30 Fluoroalkyliodonium salts, 96–98 Fluoroalkyliodonium triflimide, preparation and X-ray structure, 98 Fluoroalkyl-substituted alcohols, oxidation by catalytic sodium 2-iodobenzenesulfonate and Oxone, 362 Fluoroaryliodine(III) cyanides, preparation, properties and X-ray structure, 107 Fluorobenziodoxole, X-ray structure, 52 Fluorodeiodination, of 1-iodonorbornanes, 249 ␣-Fluoroketones, preparation from silyl enol ethers and difluoroiodotoluene, 146 3-Fluoropyridine, fluorine-18 labeled, 436, 437 3-Fluoroquinoline, fluorine-18 labeled, 436, 437 2-Fluorothiophene, preparation, 436 Fluorous aryl and alkyl iodine(III) dichlorides, preparation, 28 Fluorous techniques, 402 Formylcyclopentane, preparation from cyclohexene and PhIO•BF3 or (PhIO)3 SO3 , 174 Fragmentation of ␤-amino alcohols and ␣-amino acids, 206, 207 of tertiary cyclopropyl alcohols, 206, 208 Fredericamycin A, synthesis, 298 Fullerene C60 , azidation, 228 Furanones, 5-acetoxy-2(5H), synthesis by ring-enlargement, 208, 209 Furfuryl alcohols, 4,5-disubstituted, synthesis, 205 Furopyrano-2-isoxazoline derivatives, synthesis, 206 457 Furopyrimidinones, synthesis, 204 Furyl carbinols, synthesis, 244 (–)-Fusarisetin A, synthesis, 299 Gambieric acid A, synthesis, 299 Glycol-cleavage, with periodic acid, 303, 304 GM222712, antifungal agent, synthesis, 289 Gold-catalyzed oxidations, with hypervalent iodine reagents, 253 Green chemistry, basic principles, 381, 413 (±)-Halichlorine, tricyclic core, synthesis via alkynyliodonium salt, 272, 273 Halichondrin C, synthesis, 299 Halobenziodoxoles, 51, 52 Haloenones, synthesis by oxidative rearrangement from alkynols, 163, 164 Halogen-ate(I) complexes, polymer-supported, 387, 388 Heliannuols B and D, synthesis, 291 Heptavalent iodine, structural types, Hetaryliodonium chlorides, preparation using (E)-chlorovinyliodine(III) dichloride, 81 Heteroaryl(aryl)iodonium tosylates, preparation by [3+2] cycloaddition reactions of alkynyliodonium salts, 81, 82 using [hydroxy(tosyloxy)iodo]arenes, 78 Heteroaryliodonium salts, biocidal and antimicrobial activity, 439, 440 Heteroaryliodonium salts, X-ray studies, 82 Heteroaryl(phenyl)iodonium salts, as heteroaryl transfer agents, 262 Heteroaryl(phenyl)iodonium triflates, preparation from vinyliodonium salt and aryllithiums, 81 Heterocycles synthesis under solvent-free conditions, 420 synthesis using [hydroxy(tosyloxy)iodo]benzene, 170 synthesis using I2 as a catalyst and TBHP as oxidant, 375 Heterocyclizations, induced by hypervalent iodine reagents, 203 1H-1-Hydroxy-1,2,3-benziodoxathiole 3,3-dioxide, preparation and X-ray, 67, 68 (–)-Hispidospermidin, enantioselective total synthesis, 255, 256 Hofmann rearrangement, 213–216 hypervalent iodine-catalyzed, 355 mechanism, 215, 216 using aryl iodides as catalysts and mCPBA, 355, 356 using hypervalent iodine species generated in situ, 216 using iodobenzene and Oxone, 355, 357 458 Index Homolytic reactions of ␭3 -iodanes, 14, 15 (–)-Hopeanol and (–)-hopeahainol A, synthesis, 293 Hydrazination, organocatalytic, 348 Hydrazones conversion to alkyltosylates, 212, 213 oxidation to diazo compounds, 218 Hydroxybenziodoxaphosphole catalytic activity in hydrolysis of phosphate esters, 69 X-ray structure, 69 1-Hydroxy-1,2-benziodoxole-3(1H)-one catalytic activity in the cleavage of phosphates and reactive esters, 53 as tautomer of 2-iodosylbenzoic acid, 53 X-ray structure, 53 Hydroxybenziodoxoles, 53, 54 [Hydroxy((+)-10-camphorosulfonyloxy)iodo]benzene as reagents for enantioselective oxidation of sulfides, 220, 221 [Hydroxy(2,4-dinitrobenzenesulfonyloxy)iodo]benzene (HDNIB), reactions under microwave irradiation conditions, 421 Hydroxyiodoxolone, pKa , 70 Hydroxylation of ketones by [bis(trifluoroacetoxy)iodo]benzene, 169 metalloporphyrin-catalyzed, 250, 251 of substituted acetophenones, 169 [Hydroxy(mesyloxy)iodo]benzene study in aqueous solutions, 47 X-ray structure, 47 [Hydroxy(organosulfonyloxy)iodo]arenes chiral, 175 enantioselective reactions with alkenes, 175, 176 solvent-free preparation, 44, 45, 420 structural studies, 47 3-Hydroxy-2-oxindoles, synthesis, 205 Hydroxy(phenyl)iodonium ion, 367 [Hydroxy(phosphoryloxy)iodo]arenes, solvent-free preparation, 420 [Hydroxy(phosphoryloxy)iodo]benzenes, 49 [Hydroxy(tosyloxy)iodo]arenes chiral, 44 ion-supported, 400, 401 polymer-supported, preparation, 386–387 [Hydroxy(tosyloxy)iodo]benzene (HTIB) common names and abbreviations, 4, ESI-MS and ESI-MS/MS study, 10 ionization in solution, 10, 11 in oxidative rearrangements of alkenes, 210 polymer-supported, 45 potentiometric titrations, 10 preparation, 43–44 preparation from (diacetoxyiodo)arenes and TsOH, 43, 44 preparation, from iodoarenes, mCPBA and organosulfonic acids, 45 reactions under microwave irradiation conditions, 421 reagent for Hofmann rearrangement, 213, 215 study in aqueous solutions, 47 X-ray structure, 47 3-[Hydroxy(tosyloxy)iodo]benzoic acid, as recyclable reagent, 398 Hyperleaving group ability, of ArI group, 260 Hypernucleofuge, definition, 14 Hypervalent bond, definition, bonding, 4, bonding, in trihalide anions, 11 12-I-4 square-planar species, 14 Hypervalent iodine application in organic synthesis, complexes with nitrogen heterocycles, 109, 110 computational studies, 11, 12 experimental structural studies, history of research, 2, IUPAC nomenclature, 3, ligand coupling, 1, 13, 337 ligand exchange, 1, 13, 337 oxidative addition, 1, 337 principles of reactivity, 12 reactivity, 1, 337 reductive elimination, 1, 13 reviews and books, spectroscopic studies, typical coordination patterns, X-ray crystal structures, Hypervalent iodine catalysis, discovery of, 337 Hypervalent iodine compounds calculations of geometry and electronic structure, 12 computational studies, key structural features, 8, similarities with organometallic compounds, 7, 13, 337 synthesis, by ligand exchange, 21 synthesis, by oxidative addition, 21 typical synthetic applications, 145 Hypervalent iodine heterocycles, fused, 73, 74 Hypervalent iodine reagents chiral, for enantioselective diamination, 230 definition, general properties, nomenclature, reactions under microwave irradiation conditions, 421 solvent-free preparation, 420 Index Hypervalent molecules, Martin–Arduengo N–X–L designation, Hypervalent species, definition, Hypervalent twisting, 12 Hypoiodite-catalyzed reactions, 370–373 IBX-amides, polymer-supported, 390 IBX derivatives, as catalysts for oxidation of alcohols, 360, 361 IBX-esters polymer-supported, 390 as reagents for oxidation of alcohols, 287 Imidation of complexes of ruthenium(II), osmium(II) and cobalt(III), 260 copper-catalyzed, 257 enantioselective, of sulfides, 257–259 of nitrogen heterocycles, 256, 257 of sulfides, 256 of sulfoxides, 256, 257 of sulfur, 256 Imidazo[1,2-a]pyridines synthesis, 372 2-substituted, synthesis from alkynyliodonium salts, 271, 272 Imidazoles, synthesis, 206 Imidazolidinone, chiral catalyst, 179, 181 2-Imidazolines, synthesis, 372 Imidoiodanes, 111–114 as amidating reagents, 231, 232 soluble derivatives of ortho-alkoxyiodobenzenes, 112 for transfer the imido group to other elements in transition metal catalyzed reactions, 253 X-ray structural studies, 112, 113 ␣-Iminonitriles, one-pot synthesis by Strecker reaction, 295 (±)-Indatraline, total synthesis, 210, 211 Indazolone derivatives, synthesis, 203 Indole derivatives, N-substituted, synthesis, 204 Indole-3-methylamines, synthesis, by Hofmann rearrangement, 214 Indoline derivatives, synthesis, 203 Indolizidinones, synthesis, 203 Inorganic iodine(III) compounds, 21–23 Intermolecular interaction in hypervalent iodine compounds, 9, 11 Intramolecular C–C cyclization, iodoarene-catalyzed, 354, 355 ␭3 -Iodanes, IUPAC recommendations, 3, key structural features, 459 ␭5 -Iodanes, IUPAC recommendations, 3, key structural features, Iodanes, ␮-oxo-bridged, 47, 48 See also ␮-oxo-bridged iodanes Iodates, inorganic, as second-harmonic generation (SHG) materials, 426 metal salts, as second-order nonlinear optical (NLO) materials, 426 Iodic acid, as reagent, 302, 303 for dehydrogenation of aldehydes and ketones, 302 for deprotection of ketoximes and aromatic aldoximes, 302 for deprotection of thioacetals and thioketals, 302 for deprotection of trimethylsilyl, tetrahydropyranyl and methoxymethyl ethers, 302 for oxidation of aromatic amines to quinones, 302 for oxidation of sulfides, 302 for oxidative iodination of aromatic compounds, 302 for oxidative rearrangements and couplings, 302 Iodide anion, as pre-catalyst, 368–375 Iodinanes, general name, Iodination, of aromatics, alkenes and alkynes using IBX/I2 , 296 Iodinations, using iodine(III) reagents, 160–164 Iodine in biological organisms, bonding, coordination of, in [bis(acyloxy)iodo]arenes, 43 discovery, element, history, 1, oxidation states, pentagonal-planar coordination, 43 production, from saltpeter, production, from underground brine, in thyroid gland, Iodine(VII) structural types, synthetic applications, 303–307 Iodine(III), active catalytic species, generation from iodoarenes and Oxone, 350, 357 Iodine catalytic systems, recyclable, 406–409 Iodine(III) compounds, see also hypervalent iodine application in organic synthesis, 12, 145 general classes, 4, general reactivity pattern, 145 Iodine(V) compounds application in organic synthesis, 13, 282–303 heterocycles, 120–126 460 Index Iodine(V) compounds (Continued ) inorganic, 114, 115 inorganic reagents, 302, 303 polymer-supported, 389–391 reactions in water, 416, 417 recyclable, nonpolymeric, 405, 406 Iodine(VII) compounds, 8, 127, 128 Iodine(VII) fluoride, preparation, properties and structure, 127 Iodine fluorides, 22 Iodine(III) halides, 22, 23 Iodine(III) heterocycles aromatic character, 50 five-membered 50–71 four-membered, 50, 74 six-membered 50, 72, 73 stability, 50 Iodine (V/VII) mixed oxide, 128 Iodine(III) oxide, I2 O3 , 23 Iodine(III/V) oxides, I2 O4 and I4 O9 , 115 Iodine(VII) oxyfluorides, IO2 F3 and IOF5 , 127 Iodine–oxygen bond lengths, statistical analysis, 11 Iodine pentafluoride as fluorinating reagent, 303 as industrial fluorinating reagent, 426 as oxidant for carbon monoxide, 426 preparation and properties, 114 structure, 114 Iodine pentoxide oxidation of electron-rich alcohols in water, 303 oxidative decarboxylation of propiolic acids, 303 preparation and properties, 114 as reagent, 302, 303 structure, 115 for thiocyanation of ketones and aromatic compounds, 303 Iodine(III) reagents, see also hypervalent iodine reagents fluorous, 402–404 ionic-liquid-supported, 400, 401 magnetic nanoparticle-supported, 401, 402 polymer-supported, 381–389 recyclable, nonpolymeric, 391–404 Iodine(III) species with I–N bonds, classification, 107, 108 Iodine(III), species with three carbon ligands, 107 Iodine tribromide, 23 Iodine trichloride as chlorinating reagent, 158 discovery, preparation, 22 properties, 22, 23 stability, 22 X-ray 22, 23 Iodine trifluoride chemical properties, 22 computational studies, 22 preparation, 22 properties, 22 stability, 22 X-ray, 22 Iodine(III) tris(carboxylates), preparation and structure, 23 Iodoacetoxylation of alkenes, 161, 162 Iodobenzene as excellent leaving group, 14 magnetic nanoparticle-supported, 402 polystyrene-supported, as catalyst, 406 Iodobenzenes, ortho-substituted, as organocatalysts, 342, 343 2-Iodobenzenesulfonamide, oxidation to l-acetoxy-1,2-dihydro-1,3,2-benziodathiazole 3,3-dioxide, 69 2-Iodobenzenesulfonates, as pre-catalysts for oxidation of alcohols, 361, 362 Iodocarboxylation of alkenes, 162 2-Iodoisophthalic acid, as precursor to recyclable reagent, 396, 397 Iodolactonization hypervalent iodine-catalyzed, 344 of pentenoic acids, 205 Iodonium imides, 4, See also imidoiodanes Iodonium ion, IUPAC rules, Iodonium phenolates preparation from phenols and (diacetoxyiodo)benzene, 101 properties, 101 rearrangement by 1,4 aryl migration, 101 Iodolium salt, 74, 75 Iodonium salts biological activity, 439–443 cyclic, 74–76 definition and classification, 76 history, 76 key structural features, ligand coupling mechanism, 14 mechanism of photolysis, 427 reactions, 260–277 structure, toxicity towards mammals, 439 toxicity, 428 X-ray structural data, 76 Iodonium 8-I-2 species, in gas phase, 13 Index Iodonium transfer reaction, 81 Iodonium ylides, 4, 6, 99–106 as carbene precursors, 278–282 cyclic, 101 1,3-dicarbonyl derivatives, 99, 100 intramolecular phenyl migration, DFT study, 12 monocarbonyl, 105 preparation, 99–105 properties, 99 reactions, 278–282 reactions, catalyzed by rhodium(II) or copper complexes, 280, 281 transylidation reactions, 103 X-ray structural studies 105, 106 Iodoperfluoroalkanes, fluorous, 402 4-Iodophenoxyacetic acid, as catalyst, for oxidation of phenols, 349 Iodophosphoryloxylation of alkynes and alkenes, 162 2-Iodopyridines, preparation and properties, 405 X-ray structure, 405 as recyclable reagents, 405 2-Iodosobenzoic acid (IBA), See also 1-hydroxy-1,2-benziodoxole-3(1H)-one Iodosylalkanes, as reactive intermediates, 248, 249 Iodosylarenes NMR and LC-MS study ortho substituted, solubility, 35 ortho substituted, X-ray crystal structures, 35 preparation, by hydrolysis of acetates or chlorides, 32, 33 preparation, by oxidation of iodoarenes, 31, 32 as source of oxygen in transition metal-catalyzed oxidations, 251 structural studies, 33, 34 Iodosylbenzene aqua complexes, 13 discovery, disproportionation, 33 explosion, 33 in metalloporphyrin-catalyzed oxidations, 250, 251 monomer complexes with 18C6 crown ether, 35 oligomeric, 33 polymeric structure, 33, 34 polymer-supported, preparation, 386 reactions, 386 preparation, by hydrolysis of PhI(OAc)2 , 32 properties, 33 reactions in water, 413–416 Iodosylbenzene, activated, cleavage of alkenes, 416, 417 Iodosylbenzene, activation by bromide anion, 413, 414 Iodosylbenzene sulfate, polymer-supported, preparation and reactions, 386 Iodosylbenzene sulfates, 49 461 2-Iodosylbenzoic acid, see 1-hydroxy-1,2-benziodoxole-3(1H)-one 3-Iodosylbenzoic acid as oxidant, 284 preparation, 32 as recyclable reagent, 397–399 Iodosyl compounds polymeric structure, 31 preparation, 31 properties, 31 Iodosyl elimination, in iodosylalkanes, 248, 249 Iodosyl fluorosulfate, OIOSO2 F, preparation and properties, 23 Iodosylperfluoroalkanes, preparation, by hydrolysis of Cn F2n+1 I(CO2 CF3 )2 , 32 2-Iodosylphenylacetic acid, cyclic tautomer, 72 2-Iodosylphenylphosphoric acid, cyclic tautomer, 72, 73 Iodosyl selenate, (IO)2 SeO4 , 23 Iodosyl sulfate, (IO)2 SO4 , preparation and structure, 23 Iodosyl triflate, OIOTf, preparation and properties, 23 Iodotosyloxylation of alkynes, 161 Iodoxolones preparation, by addition of ICl3 to acetylenedicarboxylic acid, 70, 71 preparation, by oxidative cyclization of iodofumaric acid, 70, 71 X-ray structures, 70 Iodoxybenzene, see iodylbenzene 2-Iodoxybenzenesulfonic acid See also 2-iodylbenzenesulfonic acid amides, preparation and X-ray structure, 118 preparation and oxidizing properties, 124 2-Iodoxybenzoate, isopropyl in the metalloporphyrin-catalyzed oxidations, 288 as reagent, 288 2-Iodoxybenzoate, methyl ester, 117 2-Iodoxybenzoic acid (IBX) amides (IBX-amides), preparation and X-ray structure, 117 analogues of IBX, 122, 123 applications in organic synthesis, 288–296 as catalyst for oxidation of alcohols, 359, 360 dearomatization of phenols, 292 esters (IBX-esters), preparation and X-ray structure, 117 explosive properties, 121, 122 fluorous IBX, 122 generation of N-centered radicals, 294 history, 2, 121 mechanism of alcohol oxidation, theoretical study, 12 non-explosive formulation (SIBX), 122 462 Index 2-Iodoxybenzoic acid (IBX) (Continued ) o-methyl-substituted IBX (Me-IBX), 122 oxidation of alcohols, 288–291 oxidation of the benzylic carbon, 293, 294 oxidation of 1,2-diols, 291 oxidation of secondary amines to imines, 294 oxidations in ionic liquids, 419 oxidations in non-DMSO solvents, 291, 292 oxidative cyclization of anilides, 293, 294 ␣-oxygenation of carbonyl compounds, 296 pKa value, 122 polymer-supported, preparation and reactions, 390 preparation, 282, 283 preparation by bromate oxidation, 121 preparation using Oxone, 121 properties, 283 pyridinium salt, 123 six-membered cyclic IBX analogues, 124 soluble analogs (mIBX), 122 structure, 283 synthesis of amino sugars, 293 synthesis of heterocycles, 294, 295 synthesis of ␣,␤-unsaturated carbonyl systems, 293 tetrafluoro-IBX derivative (FIBX), 122 water-soluble analogs, 417, 418 X-ray structure, 121, 122 Iodylalkanes, matrix isolation and FTIR spectra, 120 2-Iodylaniline, tosyl derivative, preparation and X-ray structure, 119 Iodylarenes, 115–120 five–membered heterocyclic benziodoxole derivatives, 4, noncyclic, 4, 6, 115, 116, 283–287 ortho-phosphoryl substituted, X-ray structure, 116 preparation and properties, 116 pseudocyclic, 4, 6, 116–120, 287, 288 Iodylbenzene asymmetric oxidation of sulfides, 286, 287 cooxidant with 2-pyridineseleninic anhydride, 284 explosive properties, 116 history, 116 oxidation of alcohols, 283 oxidation of naphthols, 284 preparation and properties, 116 in the presence of VO(acac)2 , 286 X-ray structure, 116 4-Iodylbenzenesulfonate, potassium salt, preparation and properties, 405, 406 2-Iodylbenzenesulfonic acid (IBS) as catalyst benzylic oxidation, 363 as catalyst for oxidation of alcohols, 361 cyclic or pseudocyclic derivatives, 4, Iodyl fluorosulfate, 115 2-Iodylphenol ethers preparation and X-ray structure, 120 polymer-supported, 391 2-Iodylphenol, tosyl derivative, preparation, 119 2-(o-Iodylphenyl)-oxazolines, chiral, preparation and properties, 120, 288 Iodyl sulfate, 115 Iodyl triflate, 115 Iodyltrifluoromethane, preparation, 120 Ion-exchange, recycling methodology, 397 Ionic liquid, [emim]+ [BF4]− , 400 Ionic liquids, as recyclable solvents, 418, 419 Ionic-liquid-supported iodoarenes, as catalysts, 406 Ionic-liquid-supported reagents, 400, 401 Ishihara’s cycloetherification, enantioselective, 370, 371 Isoflavone derivatives, synthesis from o-hydroxychalcones, 211 Isoindolinone derivatives, synthesis, 203 Isoxazoles phenanthro-fused, by oxidative coupling, 199 synthesis, 205 Isoxazoline N-oxides, synthesis by oxidation of ␤-hydroxyketoximes, 217, 218 Isoxazolines, synthesis from aldoximes and olefins, 217 (–)-Jesterone, enantioselective synthesis, 184 Ketones, macrocyclic, synthesis by alkoxy radical fragmentation, 240, 241 Ketoximes, deoximation to ketones by HTIB, 212 Kita’s catalytic spirocyclization, 350 Koser’s reagent, 4, 5, 169 See also [hydroxy(tosyloxy)iodo]benzene (HTIB) Kryptofix (K2.2.2), 433, 434 ␤-Lactam antibiotics, synthesis, 298 Lactams, synthesis, 204 Lactols, synthesis by oxidative rearrangement reaction of 2,3-epoxy alcohols, 208 Lactones, synthesis, by radical cyclization of carboxylic acids, 239 by alkoxy radical fragmentation, 240 Lactonization, of 4-phenyl-4-pentenoic acid, 205 Lagunamycin, synthesis, 291 Lambda nomenclature, 3, L-6-[18 F]fluoroDOPA, 435 Index Ligand coupling, on the iodine atom, 13, 14 Ligand exchange dissociative and associative mechanism, 13, 14 on the iodine atom, 13, 14 Lycorane Amaryllidaceae alkaloids, enantioselective synthesis of the core, 225 Macrocyclic iodonium salts, 76 Magnetite nanoparticles, 402 (±)-Magnofargesin, synthesis via alkynyliodonium salt, 272 (±)-Makaluvamine F, synthesis, 227 (±)-Maoecrystal V, synthesis, 298 (+)-Maritidine, synthesis by phenolic spirocyclization, 189 m-chloroperoxybenzoic acid (mCPBA), as terminal oxidant in catalytic reactions, 337–356, 366, 369–371, 373, 374 [Menthyloxy(tosyloxy)iodo]benzenes, chiral, as reagents for enantioselective oxidation of sulfides, 220, 221 Metalloporphyrin-mediated oxygenations, in the presence of iodobenzene, 366, 367 Metalloporphyrins adducts with iodosylbenzene, 252 as catalysts in oxidations with iodosylbenzene, 251 (–)-Metazocine, asymmetric synthesis, 256 5-Methoxy[2.2]paracyclophan-4-yl iodonium salts, 439 2-Methoxyphenyliodonium bis(methoxycarbonyl)methanide, X-ray structure, 106 [Methoxy(tosyloxy)iodo]benzene, PhI(OMe)OTs preparation, 45 reagent for oxidative rearrangements, 212 2-Methylphenyl(2-methoxyphenyl)iodonium chloride, conformational structure, 439 mGluR5 ligands, fluorine-18 labeled, 438 m-iodosylbenzoic acid, as source of oxygen in transition metal-catalyzed oxidations, 251, 252 Moenomycin A, synthesis, 291 Monocarbonyl iodonium ylides, generation in situ and reactions, 281 Monoperoxysulfate, tetraphenylphosphonium, as terminal oxidant, 359, 360 Morphinandienone alkaloids, synthesis, 200 N-acylnitrenium intermediates, generation from amide and hypervalent iodine, 203 N-alkylsaccharins, preparation by N-radical cyclization, 247 n-butylpyridinium tetrafluoroborate, [BPy]BF4 , as a recyclable solvent, 419 463 N-hydroxysuccinimide esters, preparation from alcohols, 292 N-(2-iodylphenyl)acylamides (NIPA) polymer-supported, 390, 391 preparation and X-ray structure, 118, 119 (±)-Nitidanin, synthesis, 291 Nitriles, from aldehydes and (diacetoxyiodo)benzene, in aqueous ammonia, 417 2-Nitrobenzo[b]furans, synthesis, 205 Nitrogen heterocycles, preparation by N-radical cyclization, 247 N,N-dimethylarylamines, azidation to N-azidomethyl derivatives, 226 N,N-dimethylhydrazides, cleavage to carboxylic acids, 212 Norsesquiterpene, spirolactone/testosterone hybrid, synthesis, 209 N-tosyliminoiodanes, ArINTs as nitrene precursors in transition metal catalyzed reactions, 253 as reagents in transition metal catalyzed amidation, 255 N-tosyliminophenyliodane, PhINTs, preparation, 111 Oligomeric iodosylbenzene perchlorate, X-ray crystal structure, 34 Oligomeric iodosylbenzene sulfate, (PhIO)3 SO3 ESI-MS reactions in water, 416 as reagent for oxidation of sulfides, 218 as terminal oxidant in transition metal-catalyzed oxidations, 252 X-ray crystal structures, 34 Organoiodine(III) chlorides preparation by chlorination of organic iodides, 27 structural studies, 30, 31 Organoiodine(III) compounds, classification by type of ligands, 4, Organoiodine(V) compounds, common classes, 4, Organoiodine(V) compounds, as protein tyrosine phosphatase (PTP) inhibitors, 439 Organoiodine(III) derivatives of phosphoric acid, 49 Organoiodine(III) difluorides, 23–27 structural studies, 26, 27 Organoiodine(V) fluorides, 126, 127 Organoiodine(III) nitrate, PhI(ONO2 )2 , 48 Organoiodine(III) perchlorate, PhI(OClO3 )2 , 48, 49 Organoiodine(III) triflate, PhI(OTf)2 , 48 1-Organosulfonyloxy-1,2-benziodoxole-3(1H)-ones, preparation, 54 Ortho-effect, in reactions of diaryliodonium salts with nucleophiles, 265 464 Index Ortho-phenylation, of phenols, 262, 263 1,3,4-Oxadiazoles, 2,5-disubstituted, synthesis, 206 1,2,4-Oxadiazoles, synthesis, 204 Oxazole derivatives, synthesis, 372, 375 Oxazolines, 2-substituted, synthesis, 206 Oxidation of alcohols by 1-chloro-1,2-benziodoxol-3(1H)-one/TEMPO, 167 1,2-diols, 167 with DMP, 296–299 epimerization-free, 298 (fluoroalkyl)alkanols, to aldehydes, 166 by HTIB under solvent-free microwave irradiation, 167 with IBX, 288–291 by iodine(III) reagents, 164–168 by iodosylbenzene/KBr, 164, 165 with Oxone, catalyzed by PhI and RuCl3 , 367, 368 by PhICl2 /TEMPO, 167 by PhI(OAc)2 /I2 , 165 by PhI(OAc)2 /NaBr, 165 by PhI(OAc)2 /TEMPO, 165–167 with potassium peroxodisulfate, catalyzed by PhI and TEMPO, 366 in the presence of Wittig ylide, 166, 291, 298 transition metal catalyzed, 167 Oxidation of alkylbenzenes, with Oxone, catalyzed by PhI and RuCl3 , 367, 368 Oxidation of anilines, hypervalent iodine-catalyzed, 357 Oxidation of iodoarene, to aryliodine(III) in situ, 337, 338 Oxidations of antimony, 222 of bismuth, 222 of C–H bonds, at the benzylic or allylic position, 181, 182 of nitrogen, 216–218 with PhIO/Bu4 NI in water, 415, 416 of sulfur, 218 transition metal catalyzed, 250 using catalytic Bu4 NI and TBHP as oxidant, 369 Oxidative amination, of arenes, hypervalent iodine-catalyzed, 347, 349 Oxidative bromination, of arenes, hypervalent iodine-catalyzed, 346 Oxidative brominations, using iodine(III) reagent and bromide, 158, 159 Oxidative cleavage, of alkenes and alkynes, hypervalent iodine-catalyzed, 345 Oxidative coupling of aromatic substrates, 196–201 of Bodipy monomers, 201, 203 of cycloalkenylsilanes with silylated nucleobase, 200, 203 in intramolecular mode, 197–201 of ketones with carboxylic acids, 369 of Michael adducts, by PhIO/Bu4 NI in water, 415 mechanism 196, 197 of non-phenolic aromatic substrates, 200, 202 Oxidative cyclizations, 201 Oxidative cycloetherification, of oxo-substituted phenols with Bu4 NI/H2 O2 , 370 enantioselective, 370 Oxidative dearomatization of anilines, 195, 196 catalytic, 350 formation of cyclohexadienones, 195, 196 in the intramolecular mode, 187 mechanism, 196 of phenols, 183–195 in the presence of carbon nucleophiles, 187 in the presence of fluoride anion, 187 of 2-substituted phenols, 193–195 using (diacetoxyiodo)benzene in methanol, 184, 185 Oxidative decarboxylation, of 2-aryl-substituted carboxylic acids, 206 Oxidative decarboxylation/iodination of carboxylic acids, 162 Oxidative fragmentations, 201, 206 Oxidative functionalization, hypervalent iodine-catalyzed, 342–346 Oxidative iodination of alkanes, with the PhI(OAc)2 –iodine system, 160 of aromatic and heteroaromatic compounds, 160, 161 of electron-deficient heterocyclic systems, 160 of ketones, 162 of terminal alkynes, 163 using tosyloxybenziodoxole-iodine system, 161 Oxidative phenolic cyclizations, in the synthesis of acetylaspidoalbidine, 192 (–)-cylindricine C and (–)-2-epicylindricine C, 192 dihydrofuranobenzofurans, 192 discorhabdin A, 192 galanthamine, 192 platensimycin, 192 (+)-plicamine, 192 tuberostemonine and didehydrotuberostemonine, 192 Oxidative rearrangements, 201, 206 Oxidative spirocyclization of amides and ketoximes, 187 of catechol, 187 enantioselective, 353 in enantiospecific synthesis of (+)-puupehenone, 187 hypervalent iodine-catalyzed, 350–354 of N-protected tyrosine, 187 Index of phenolic substrates, 187 in synthesis of annosqualine, 190 in synthesis of cortistatin class of natural products, 188 in synthesis of furoquinolinone and angelicin derivatives, 188 in synthesis of nitrogen heterocycles, 188 in synthesis of (±)-stepharine, 190 10-Oxidophenothiiodonium salt, 74, 75 Oximes, oxidation to nitroso compounds, 218 ␤-Oxoalkyl(phenyl)iodonium salts, generation from silyl enol ethers, 96, 97, 275 ␮-Oxo-bridged iodanes mesylate, 47 nitrate, 49 perchlorate, 48 tetrafluoroborate, 48 triflate, 48 trifluoroacetate, 49, 192, 417 (9-Oxo-9H-fluoren-2-yl)phenyliodonium hexafluoroantimonate, as photoinitiator, 42 Oxoindoles, 3,3-disubstituted, synthesis, 343 (±)-Oxomaritidine, synthesis, 385 Oxone (2KHSO5 ·KHSO4 ·K2 SO4 ), in oxidation of iodobenzene, 32 Oxone, as terminal oxidant in catalytic reactions, 337, 340–343, 349–351, 355–368 ␣-Oxyacylation, Bu4 NI-catalyzed, 369 Oxygen heterocycles, synthesis by oxidative cyclizations, 205 Oxylactonization, enantioselective with Bu4 NI as pre-catalyst and H2 O2 as oxidant, 369 of ketocarboxylic acids, hypervalent iodine-catalyzed, 339 of ortho-alkenylbenzoates, 179 Pachastrissamine, synthesis, 291 p-Alkoxyphenols, oxidative dearomatization, by (diacetoxyiodo)benzene, 184, 185 Palladacycles, reactions with aryliodonium imides, 257 (+)-Pancratistatin, total synthesis, 225 Passerini reaction, 295 Pd-catalyzed oxidations, with hypervalent iodine reagents, 252 (+)-Peloruside A, synthesis, 298 Pentafluoroethylbenziodoxolone, 61 Pentafluorophenyliododifluoride, C6 F5 IF2 , X-ray and spectroscopy studies, 27 Pentavalent iodine, structural types, 3, Perfluoroalkyliodine(V) fluorides, preparation and X-ray structure, 126 465 Perfluoroalkyl(phenyl)iodonium triflates (FITS reagents) as electrophilic perfluoroalkylating reagents, 275, 276 preparation, 97 Periodate oxidation, application in chemical and instrumental analysis, 426 Periodates, 128 Periodate salts, as oxidizers in pyrotechnic formulations, 426 Periodic acid glycol-cleavage, 303, 304 as oxidant, 426 oxidative cleavage of protecting groups, 305 oxidative iodination of aromatic compounds, 305 properties and structure, 128 as reagent, 303–305 synthesis of nitriles from alcohols or aldehydes, 305 transition metal catalyzed oxidations, 304, 305 Periodinanes, general name, 4,5-Phenanthryleneiodonium salts, 74, 75 Phenol ethers intramolecular cyclization of azido derivatives 199, 200 nucleophilic substitution using hypervalent iodine, 197 oxidative coupling, hypervalent iodine-catalyzed, 354 Phenols oxidation to benzoquinones, hypervalent iodine-catalyzed, 349 oxidation to o-quinones, by IBX, 292 oxidation to o-quinones, iodine(V) catalyzed, 364 p-substituted, oxidation to p-quinols, 350 Phenoxiodonium salt, 74, 75 Phenylbenziodazole, preparation and X-ray structure, 63 1-Phenyl-1,2-benziodoxole-3(1H)-one, preparation, 59–60 Phenyl(cyano)iodonium triflate, preparation and application as the iodonium transfer reagent, 95 Phenyl(3-formylphenyl)iodonium salts, synthesis and 18 F-fluoridation, 438, 439 Phenylhydrazones, regeneration of carbonyl, 218 Phenyliodonium imide ortho-methoxy substituted, X-ray structure, 113 ortho-sulfonyl substituted, X-ray structure, 113 polymeric structure, 113, 114 Phenyliodonium, leaving group ability, 267 Phenyliodonium ylides, X-ray structures Phenyl[2-(trimethylsilyl)phenyl]iodonium triflate, as benzyne precursor, 266 Phosphonium–iodonium ylides preparation and X-ray structure, 104 reactions, 282 466 Index Phosphoranyl-derived benziodoxoles, preparation and X-ray structure, 60 Phosphoryloxylactonization, hypervalent iodine-catalyzed, 344 ␣-Phosphoryloxylation of ketones, iodobenzene-catalyzed, 342 Photoacid generators (PAGs), 427 Photoinitiators, for cationic photopolymerizations, 426 Photopolymerization, 427 Photoresist technology, 426 Photosensitivity, of iodonium salt, 427 Physostigmine, synthesis, 344 (–)-Pinidine, asymmetric synthesis, 207 (±)-Platensimycin, synthesis, 298 (–)-Platensimycin, synthesis by oxidative Prins–pinacol tandem process, 191 p-nitro(dichloroiodo)benzene, chlorination of pyrrolidine, 156, 157 Poly[(diacetoxyiodo)styrene] applications, 383–386 oxidation of alcohols, 384 oxidation of glycols, 384 oxidation of phenols, 384, 385 oxidation of sulfides, 384 oxidative iodination, 384 preparation, 382, 383 synthesis of heterocycles, 385 synthesis of organyltellurophosphates, 386 Poly[(dichloroiodo)styrene] as chlorinating reagent, 381, 382 preparation, 381 Poly(ethylene glycol-400), PEG-400, as a recyclable solvent, 419 Poly[hydroxy(tosyloxy)iodo]styrene, synthetic applications, 387 Polymerization, dual photo- and thermal-initiation systems, 427, 428 Polymer-supported reagents, general application, 381 Polystyrene, azidation and click-type functionalization, 228, 431 Polyvalent iodine, see hypervalent iodine Polyvalent iodine compounds, see also hypervalent iodine compounds classification, 3, commercial availability, 425 common abbreviations, 4, common names, 4, IUPAC nomenclature, 3, practical applications, 425 Positron emission tomography (PET), 431, 432 Potassium iodate as dietary supplement and a food additive, 425 as source of iodine in iodized salt, 425 toxicity, 425, 426 Prins–pinacol, oxidative tandem process, 190, 191 Pseudocyclic iodylarenes, polymer-supported, 390, 391 (–)-Pseudolaric acid B, synthesis, 298 Pseudopterosin and elisabethin, analogs, synthesis, 301 Pseudorotation on the iodine atom, 9, 10, 14 (±)-Pterocarpans, synthesis, 291 Pyridine derivatives, synthesis, 375 2-Pyridyldiselenide, as reagent, 285 Pyrimidines, phenanthro-fused, by oxidative coupling, 199 Pyrroles, polysubstituted, synthesis, 206 Pyrrolidines, 2-substituted, synthesis, 239 Pyrrolidino[60]fullerene, synthesis, 204 Pyrrolidinone derivatives, synthesis, 203 Pyrrolin-4-ones, synthesis, 204 Pyrrolo(benzo)diazepines, synthesis, 204 Pyrrolo[2,1-c][1,4]diazepines, synthesis, 203 Pyrroloiminoquinone system, by intramolecular coupling of azido derivatives, 199 Quaternary ammonium iodide catalyst, chiral, 370 Quaternary carbon center, by oxidative ipso-rearrangement, 191, 192 Quinazolines, synthesis, 375 Quinolinone derivatives, synthesis, 203 Radical alkylation of alkenes, 237, 238 of nitrogen heterocycles, 237, 238 Radical cyclizations, 236, 239, 247 Radical fragmentation–phosphorylation, 246 Radical fragmentations, 236–248 Radical reactions of ␭3 -iodanes, 14, 15 Radical rearrangements, 236, 239–248 Radicals generation from amides and iodosylbenzene, 247, 248 nitrogen-centered, generation, 247, 248 oxygen-centered, generation, 238–244 Radiofluorination, of diaryliodonium salts, 432 Reactions in water, 413–418 Recyclable nonpolymeric reagents, separation techniques, 391 Recyclable organic solvents, 418–420 Recyclable reagents biphenyl, 394–396 derivatives of 1,3,5,7-tetraphenyladamantane, 394–396 Index terphenyl, 394–396 tetraphenylmethane, 394–396 Reductive elimination of PhI, 13, 14 Resolvin D1, synthesis, 299 Resveratrol, diacyl derivatives, hydroxylation, 296 Ring expansion in reactions of HTIB, with alkenes, 212 reactions, promoted by hypervalent iodine, 207 in reactions of 1-vinylcycloalkanol derivatives, 212 Ripostatin B, synthesis, 299 (+)-Ritterazine K, synthesis, 298 Salvinorin A, synthesis, 298 Sceletenone, total synthesis, 191 Secondary bonding in hypervalent iodine compounds, 9, 11 Secondary bonds, in [bis(acyloxy)iodo]arenes, 43 Seco-psymberin/irciniastatin A, synthesis, 206 Selenodecarboxylation, 236 Self-assembly of hypervalent iodine compounds, 9, 11 SET mechanism, in reactions of ␭3 -iodanes, 15 SET mechanism, in reactions of ␭5 -iodanes, 15 (+)-Sieboldine A, synthesis, 299 Silica-supported iodoarenes, as catalysts, 406 Silylalkenes, reaction with PhIO•BF3 , 175 Silyl enol ethers, oxidative functionalization preparation of 1,4-butanediones, 172 preparation of ␤-keto phosphonates, 172 preparation of ␣-methoxylated esters and lactones, 173 preparation of oxygen heterocycles, 172 preparation of ␣-substituted ketones, 171, 172 preparation of ␣-trifluoromethanesulfonyloxyketones, 172 ␣-tosylamination, 231, 232 Single-electron transfer (SET) mechanism, 15 SiO2 -supported RuCl3 , as recyclable catalyst, 393 (S)-Ketoprofen, synthesis, 266 Sodium metaperiodate, NaIO4 for azidoiodination of alkenes, 306 for carbonylation of benzylamines, 306 for diazidation of alkenes, 306 for glycol-cleavage, 305 for oxidation of alcohols to carbonyl compounds, 305 as reagent, 305–307 for transition metal catalyzed oxidations, 306, 307 Solvent-free reactions, 420–422 Somamide A, synthesis, 291 Spiculoic acid A, synthesis, 291 Spirastrellolide A, synthesis, 299 Spirocyclization, of 2-substituted phenols, enantioselective, 193, 194 467 Spirofurans and benzopyrans, iodobenzene-catalyzed synthesis, 352 Spiroketalization of phenolic alcohols, DFT calculations, 12 Spirolactams, synthesis by catalytic spirocyclization, 353 by oxidative spirocyclization, 188 Spirolactones, preparation from phenolic substrates, 350 Spirooxindoles, synthesis, 205, 355 (–)-Spirotryprostatin B, synthesis, 298 Steroidal derivatives, synthesis by alkoxy radical fragmentation, 240, 241, 244 Steroidal substrates, oxidative transformations, 209, 210 (–)-Subincanadines A and B, synthesis, 291 Sulfate esters, cyclic, preparation, 176, 177 Sulfides ␣-azidation, 227 enantioselective oxidation, 220 oxidation to sulfonyl chlorides, 219 oxidation to sulfoxides, 218 Sulfonylation, allylic, of ␣-methyl styrenes, 373, 374 Sulfonyloxylactonization, hypervalent iodine-catalyzed, 344 Sulfoxides, chiral, by enantioselective oxidation of sulfides, 220, 221 Tagged hypervalent iodine reagents, 397 Tandem catalytic systems, based on hypervalent iodine, 364–368 TEMPO ion-supported, 400 as radical scavenger, in reactions of diaryliodonium salts, 434, 435 TEMPO-catalyzed oxidations, 166 4-Tert-butyl(difluoroiodo)benzene, fluorination of esters of cephalosporin, 146, 148 Tert-butyl hydroperoxide (TBHP), as terminal oxidant, 369, 371–375 1-(Tert-butylperoxy)benziodoxoles, preparation 55 X-ray structure, 55 1-(Tert-butylsulfonyl)-2-iodylbenzene, preparation and X-ray structure, 116 Tertiary allylic alcohols, rearrangement to enones, iodine(V) catalyzed, 362 Tetrachloroiodate salts, as chlorinating reagents, 158 (Tetrafluoroiodo)benzene, C6 H5 IF4 , preparation, properties and X-ray structure, 126 Tetrahydroisoquinolines C–H functionalization, 377 synthesis by Ugi-type multicomponent reaction, 295 468 Index Tetrahydropyrans, 2-(N-acylaminal) substituted, synthesis, 206 (–)-Tetrodotoxin, synthesis using PhIO2 /Py2 Se2 , 285 1,2,4-Thiadiazoles, synthesis, 204 Thiazoles 2,4-disubstituted, synthesis from alkynyliodonium salts 272 phenanthro-fused, by oxidative coupling, 199 Thiazolo-fused quinolinones, synthesis, 203 Thienyl iodonium salts, preparation by iodonium transfer using PhI(CN)OTf, 81 Thioacetals, cleavage to carbonyl compounds, 221 Thiocyanation, of indoles, pyrrole and arylamines, 296 Thiocyanations, 232–235 Thioketals, cleavage to carbonyl compounds, 221 Thiophene dimers, preparation, by oxidative coupling of 3-substituted thiophenes, 200, 202 Thiosulfonic S-esters, preparation by oxidation of diaryl disulfides or thiophenols, 219, 220 Three–center–four–electron (3c – 4e) bond, 1, Thyroxine, (–)-Tirandamycin C, synthesis, 299 Tosyliminoiodane, PhINTs aziridination of alkenes, 253 reagent for Hofmann rearrangement, 215 ␣-Tosyloxylation of ketones enantioselective, catalyzed by chiral iodoarenes, 341 iodobenzene-catalyzed, 339, 340 NH4 I-catalyzed, 370 p-iodotoluene-catalyzed, 340 in the presence of a catalytic I2 , 340 under solvent-free conditions, 420 ␣-Tosyloxyketones from alcohols, by oxidation–tosyloxylation, 170 preparation from ketones and HTIB, 169, 170 Trans influence in hypervalent iodine(III) compounds, 7, 11 in hypervalent iodine(V) compounds, 11 quantitative measurement, 11 Trans-2-aminocyclohexanecarboxylic acid, synthesis, by Hofmann rearrangement, 215 Triaryliodanes, 107 Triaryl-␭3 -iodanes, low-temperature NMR studies, 9, 10 [1,2,4]Triazolo[4,3-a][1,4]benzodiazepine derivatives, synthesis, 206 1,2,4-Triazolo[4,3-a]pyrimidines, synthesis, 204 Trifluoromethylation asymmetric, in the presence of imidazolidinone catalyst, 277 of C-nucleophiles, 277 of ␤-ketoesters, 276, 277 of N-nucleophiles, 277 of P-nucleophiles, 277 of S-nucleophiles, 277 Trifluoromethylbenziodoxoles, 60–62 from 2-iodobenzoic acid, 60 from methoxybenziodoxole or acetoxybenziodoxole, 60 as reagents for the trifluoromethylation, 61, 276, 277 X-ray structures, 60, 61 (Trifluoromethyl)iodine dichloride, CF3 ICl2 CF3 ICl2 , X-ray crystal structure, 31 preparation, 29 Trifluoromethyliododifluoride, CF3 IF2 theoretical studies, 26 X-ray structure, 26, 27 Triisopropylsilyl enol ethers, azidation to ␤-azido adducts, 224, 225 1-[(Triisopropylsilyl)ethynyl]-1,2-benziodoxol-3(1H)one (TIPS-EBX), 59 1,3,5-Trioxocane derivatives, synthesis, 244 Triphenyl iodine, Ph3 I, 107 Tris(alkynyliodonium) salts, 92 Trivalent iodine, structural types, 3, Twisted IBX, as catalyst for oxidation of alcohols, 361 ␣,␤-Unsaturated carbonyl compounds, synthesis by IBX oxidation, 293 Valienamine, synthesis via iodosyl elimination, 249 Vinyliodonium ions, ab initio MO calculations of reactivity, 12 Vinyl sulfones, chiral, synthesis by alkoxy radical fragmentation, 241 Wighteone, regioselective synthesis, 210, 211 Ylides of 2,4-dihydroxyacetophenones, preparation, 103 of hydroxycoumarins, preparation and structure, 101 of hydroxyquinones, preparation, 102 aza analogues, 102 Ynamides, by amination of terminal alkynes, 231 Zwitterionic iodonium compounds, 101 ... Hypervalent Iodine Chemistry Hypervalent Iodine Chemistry Preparation, Structure and Synthetic Applications of Polyvalent Iodine Compounds Viktor V Zhdankin Department of Chemistry and Biochemistry... centuries of iodine research was published in 2011 by Kuepper and coauthors [9] Hypervalent Iodine Chemistry: Preparation, Structure and Synthetic Applications of Polyvalent Iodine Compounds, ... herefrom Library of Congress Cataloging-in-Publication Data Zhdankin, Viktor V., 1956– Hypervalent iodine chemistry : preparation, structure and synthetic applications of polyvalent iodine compounds