Catalytic Oxidation Reagents

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

Professor Philip L. Fuchs, Department of Chemistry, Purdue University
Philip Fuchs began his career at Purdue in 1973. Since that time, he has graduated an extended family of 55 Ph.D.s. His awards and honors include an Eli Lilly young faculty fellowship (1975), an Alfred P. Sloan fellowship (1977), a Pioneer in Laboratory Robotics award (1986), a Martin teaching award (1991), and being voted by the students as one of Top 10 Teachers in School of Science at Purdue (1991, 1993, 1995, 1996).
Fuchs has consulted for Pfizer, and Eli Lilly, served on the editorial board of The Journal of Organic Chemistry, and is currently an executive editor for the Electronic Encyclopedia of Organic Reagents (e-EROS), an online dynamic encyclopedia published by John Wiley & Sons.

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

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