The Handbook is part of the Handbook of Reagents for Organic Chemistry series, aiming at collecting articles on a particular theme that individual researchers in academia or industry can use on a daily basis.
The Handbook starts with a section discussing the most important aspects of heteroarene functionalization. The introduction is followed by the alphabetical listing of the most relevant reagents drawn from the EROS database. The Editor, André Charette from the University of Montreal, has selected 120 reagent descriptions, many of them updated with heteroarene-specific reactions for this Handbook. Following the standard format for EROS, each article contains an overview of the synthesis and physical properties of the reagents or catalyst, conditions for its storage, and purification methods.
Given the importance of heteroarenes in biology and especially in medicinal chemistry, a Handbook that focuses exclusively on heteroarene functionalization has been long overdue. This Handbook will have a broad appeal to many individuals engaged in the area of medicinal chemistry, fine chemical synthesis and industrial-scale chemistry.
Key features:
- Builds on the success of the previously published Handbooks of Reagents for Organic Synthesis
- Compares the numerous new C-H functionalization reactions that have been developed in the past decade
- Heteroarene functionalization is widely used in the development of pharmaceuticals and other bioactive compounds
- Contains listings of secondary reagents for which more information is available in the online edition
Table of Contents
Preface xi
Introduction xiii
Terminal Oxidants Finder xv
Oxidation Catalyst Finder xix
Recent Review Articles and Monographs xxv
Short Note on InChIs and InChIKeys xxvii
4-Acetamido-2,2,6,6-tetramethyl-1-piperidinyloxyl 1
4-Acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium Tetrafluoroborate 2
Bathocuproine 15
Bathophenanthroline 17
Benzenecarboperoxoic acid, 1, 1-dimethylethyl Ester 20
1,2-Benziodoxol-3(1H)-one, 1-Hydroxy, 1-Oxide, IBX 32
1,2-Benziodoxol-3(1H)-one, 1-Hydroxy, 1-Oxide, stabilized (stabilized IBX) 44 1,4-Benzoquinone 49
cis-4-Benzyloxy-α,α-bis-(3,5-dimethylphenyl)-Lprolinol (2S,4R)- 52
2,2_-Bipyrrolidines, (2S,2_S) and (2R,2_R) 54
2-[Bis-[3,5-bis(trifluoromethyl)Phenyl] [(trimethylsilyl)oxy]Methyl]Pyrrolidine 57
2,2-Bis[2-[4(S)-tert-butyl-1,3-oxazolinyl]]propane 59
Bis[[(1R,1__R)-3,3__-[(1R,2R)-1,2-cyclohexanediylbis [(nitrilo-κN)methylidyne]]bis[2_-phenyl[1,1_-
binaphthalen]-2-olato-κO]](2-)]di-μ-oxodi-titanium and Bis[[(1S,1__S)-3,3__-[(1S,2S)-1,2- cyclohexanediylbis[(nitrilo-κN)methylidyne]]bis [2_-phenyl[1,1_-binaphthalen]-2-olato-κO]](2-)]di- μ-oxodi-titanium 66
Bis(2,2-dimethylpropanoato - κ-O)phenyl-iodine 69
Bis(1-methyl-1-phenylethyl) Peroxide 77
1,2-Bis(phenylsulfinyl)ethane 79
N,N_-Bis(2,4,6-trimethylphenyl)imidazol-2-ylidene Palladium(I) Allyl Chloride 82
Bis(trimethylsilyl) Peroxide 87
Bromamine-T 91
N-tert-Butyl-N-chlorocyanamide 94
tert-Butyl Hydroperoxide 96
tert-Butyl Hypochlorite 126
tert-Butyl Peracetate 132
Calcium Hypochlorite 137
Chloramine-T 142
Chlorobenzene 150
Chloro[N,N_-ethylenebis(salicylideneaminato)] manganese 152
Chromium(VI) Oxide 157
Chromyl Acetate 163
Cobalt, [5,10,15,20-tetraphenyl-21H,23Hporphinato( 2−)-κN 21,κN 22,κN 23,κN 24]- 167
Cumyl Hydroperoxide 171
N,N_-(1R,2R)-1,2-Cyclohexanediylbis- [N-hydroxy-α-phenybenzeneacetamide] 179
1,5-Diaza-cis-decalin 183
N,N-Dibromobenzenesulfonamide and N,N-Dibromo-p-toluenesulfonamide 188
Di-μ-chlorobis(1,5-cyclooctadiene)diiridium(I) 195
Di-μ-chlorodichlorobis[(1,2,3,4,5-η)-1,2,-3,4,5- pentamethyl-2,4-cyclopentadien-1-yl]diiridium 202
(R)-2,10-Dichloro-5H-dinaphtho[2,1-g: 1,2-i][1,5]dioxacycloundecin-3,6,9(7h)-trione 210
Dichloro(ethoxy)oxovanadium(V) 213
1,1_-Difluoro-2,2_-bipyridinium Bis-(tetrafluoroborate) 217
1,2:4,5-Di-O-isopropylidene-β-d-erythro-hexo-2,3- diulo-2,6-pyranose 221
Di-μ-methoxobis(1,5-cyclooctadiene)diiridium(I) 224
Dimethyldioxirane 228
(S,S)-2,2_-(Dimethylmethylene)bis(4-tert-butyl-2- oxazoline) and (R,R)-2,2_-(Dimethylmethylene)bis- (4-tert-butyl- 2-oxazoline) 234
Dispiro[2H-pyran-2,4_-[4H-5,6,8b]triazaacenaphthylene- 7_(5_H),2__-[2H]pyran], 1_,2_,2_a,3,3_,3__,4,4__,5,5__,
6,6__,8_,8_a-tetradecahydro-1_,2_-dimethoxy-6,6__- dimethyl-, monohydrochloride, (1_S,2R,2_S,2__R, 2_aS,6S,6__S,8_aS)- 257
N-fluoro-N-(phenylsulfonyl)-benzenesulfonamide 259
N-Fluoropyridinium Tetrafluoroborate 270
N-Fluoropyridinium Triflate 272
1-Fluoro-2,4,6-trimethylpyridinium Tetrafluoroborate 274
1-Fluoro-2,4,6-trimethylpyridinium Trifluoromethanesulfonate 278
Hydrogen Peroxide 281
Hydrogen Peroxide–Urea 295
N-Hydroxyphthalimide 307
Iodine 317
2-Iodobenzenesulfonic Acid 332
Iodosylbenzene 338
Iridium, [N-[(1R,2R)-2-(amino-κN)-cyclohexyl]-4- methylbenzenesulfonamidato-κN]chloro[(1,2,3,4,5-η)-
1,2,3,4,5-pentamethyl-2,4,- cyclopentadien-1-yl]-; Iridium, [N-[(1R,2R)-2-(amino-κN)- cyclohexyl]-4-
methylbenzenesulfonamidato-κN]chloro[(1,2,3,4,5-η)- 1,2,3,4,5-pentamethyl-2,4,-cyclopentadien-1-yl]-; Iridium, [N-[(1S,2S)-2-(amino-κN)cyclohexyl]-4- methylbenzenesulfonamidato-κN]-chloro [(1,2,3,4,5-η)-1,2,3,4,5-pentamethyl-2,4,-
cyclopentadien-1-yl]- 354
Iridium, Dichlorodi-μ-hydrobis[(1,2,3,4,5-η)- 1,2,3,4,5-pentamethyl-2,4-cyclopentadien-1-yl]di- 357
Iron, Bis(pyridine)bis(2-pyridinecarboxylato-N1,O2) 359
Lithium Hydroperoxide 363
Manganese(III) Acetate 367
Manganese(II), bis(octahydro-1,4,7-trimethyl-1H-1,4,7- triazonine-κN1,κN4,κN7)tri-μ-oxodi-, hexafluorophosphate 375
Manganese(II) tetraphenylporphyrin 378
9-Mesityl-10-methylacridinium Perchlorate 381
N-Methylmorpholine N-Oxide 384
(S)-(−)-4-(2-Methylpropyl)-2-(2-pyridyl)-2-oxazoline 388
Methyl(trifluoromethyl)dioxirane 390
Methyltrioxorhenium 396
Molybdenum Chloride Oxide 407
Noyori Oxidation (Sodium Tungstate Dihydrate, Hydrogen Peroxide, Methyltri-n-octylammonium Hydrogen Sulfate, Phosphonic Acid) 411
3,3_,3α,3α _,4,4_,5,5_-Octahydro-3,3,3_,3_-tetraisopropyl- 6,6_-spirobi-[6H-cyclopent[c]isoxazole] 415
4,4,4_,4_,5,5,5_,5_-Octamethyl-2,2_-bi-1,3,2-dioxaborolane 421
Osmium Tetroxide 433
μ-Oxo-bis[tetrakis(t-butyl)-phthalocyaninatoiron(III)] 452
Oxygen 454
Palladium (II) Sparteine Dichloride 467
Peracetic Acid 470
(8α,9R)-(8__ α,9__R)-1,1__-[1,3-Phenylene-bis(methylene)] bis[9-hydroxy-cinchonanium] Dibromide and (9S)-(9__S)-1,1__-[1,3-Phenylene-bis(methylene)] bis[9-hydroxy-cinchonanium]Dibromide 478
(−)(1S)-1-Phenylethyl Hydroperoxide and (+)(1R)-1-Phenylethyl Hydroperoxide 480
(8α,9R)-(8__ α,9__R)-9,9__-[1,4-Phthalazinediylbis(oxy)] bis[10,11-dihydro-6_-methoxycinchonan] & (9S)-(9__S)-9,9__-[1,4-Phthalazinediylbis(oxy)] bis[10,11-dihydro-6_-methoxycinchonan] 483
Picolinic Acid 495
Polyaniline 498
Potassium Bromate 502
Potassium Monoperoxysulfate 506
2-Pyrazinecarboxylic Acid 524
2,3-Pyrazinedicarboxylic Acid 530
Pyrrolidine, 3,4-bis(diphenylphosphino)-1- (phenylmethyl)-,(3R,4R) and Pyrrolidine, 3,4-bis(diphenylphosphino)-1-(phenylmethyl)-, (3S,4S) 532
2-Pyrrolidinemethanol-α,α-bis(3,5-dimethylphenyl)- (2S); and 2-Pyrrolidine-methanol-α,α-bis(3,5- dimethylphenyl)-(2R) 535
Rhenium(VII) Oxide 541
[RuCl2(p-cymene)2]2 546
Ruthenium(III) Chloride 549
Ruthenium Complex of N,N_,N_-Trimethyl-1,4,7-triazacyclononane and Ruthenium Complex of cis-Diaquabis
(6,6_-Dichloro-2,2_-bipyridine) 561
Ruthenium Dodecacarbonyltri Triangulo 565
Ruthenium Hydroxide 568
Selenium(IV) Oxide 575
Sodium Bromate 583
Sodium Hypochlorite 587
Sodium Hypochlorite–N,N_-Bis(3,5-di-tertbutylsalicylidene)- 1,2-cyclohexanediaminomanganese( III) Chloride 600
Spiro[6H-1,3-dioxolo[4,5-c]pyran-6,5_-oxazolidine]-3_- carboxylic acid, tetrahydro-2,2-dimethyl-2_,7- dioxo-,2-methyl-2-propyl ester, (3aR, 5_S, 7aR)- 604
Tetrabutylammonium Bis(pyrazinecarboxylato)- dioxo-vanadium(V) 609
Tetrabutylammonium Dodecatungstophosphate 611
Tetrabutylammonium Peroxydisulfate 615
5,6,7,8-Tetrafluoro-1-hydroxy-1-oxobenziodoxol- 3(1H)one (Tetrafluoro-IBX) 618
2,2,6,6-Tetramethylpiperidin-1-oxyl 620
Tetra-n-propylammonium Perruthenate 626
3,3_,5,5_-Tetra-tert-butyldiphenoquinone 630
(S)-2-(5-1H-Tetrazolyl)pyrrolidine and (R)-2-(5-1H-Tetrazolyl)pyrrolidine 633
4,4_,4__-tri-tert-butyl-2,2_:6_,2__-terpyridine 639
Trichloroisocyanuric Acid 642
Trifluoroperacetic Acid 649
Trimethylamine N-Oxide 659
Triphenylmethyl Hydroperoxide 667
Tris(2-pyridylmethyl)amine 670
Tris[4-(trifluoromethyl)phenyl]phosphine 677
Vanadium,bis[N-[(1S)-1-(carboxy-κO)ethyl]-N- (hydroxy-κO)-l-alaninato(2-)-κN,κO]- 681
Vanadyl Bis(acetylacetonate) 684
List of Contributors 693
Reagent Formula Index 707
Subject Index 711
