Handbook of Reagents for Organic Synthesis Reagents for Heteroarene Functionalization

Heteroarenes are among the most prevalent structural units in natural products, pharmaceuticals, agrochemicals, and other compounds of scientific or commercial interest. In the last decade, a broad range of novel synthetic methods has been developed to not only facilitate construction of the heteroarene motif, but to enable its modification through direct C?H functionalization. This Handbook describes 117 key reagents for selective heteroarene functionalization reactions, including both traditional and transition metal-catalyzed C?H functionalization. Since these reactions typically involve one heteroarene, a coupling partner and a catalyst, the handbook not only focuses on the catalyst itself but also contains other key reaction species.

All the information compiled in this volume is also available in electronic format on Wiley Online Library. The 117 reagents represented here are but a small fraction of the ca. 5,000 reagents available in the electronic Encyclopedia of Reagents for Organic Synthesis (e-EROS). e-EROS offers various search interfaces to locate reagents of interest, including chemical structure, substructure and reactions search modes. e-EROS is updated regularly with new and updated entries.

Preface ix

Introduction xi

Recent Review Articles and Monographs xiii

Short Note on InChIs and InChIKeys xv

Acetic Anhydride 1

Acetyl Chloride 8

Aluminum Chloride 18

Aluminum Trifluoromethanesulfonate 25

Antimony Trifluoromethanesulfonate 29

Bathophenanthroline 31

1,2-Benzodiazine 34

Benzopyrazole 35

Benzotriazole 39

Bis(allyl)di-μ-chlorodipalladium 42

Bis(benzonitrile)dichloropalladium(II) 66

Bis(dibenzylideneacetone)palladium(0) 92

Bis(1,10-phenanthroline)palladium

Hexafluorophosphate 107

Bis[tris(1,1-dimethylethyl)-phosphine]palladium 109

Bromine 112

N-Bromosuccinimide 117

n-Butyllithium 127

sec-Butyllithium 143

tert-Butyllithium 155

Butyllithium–Potassium tert-Butoxide 164

Cesium Acetate 173

N-Chlorosuccinimide 175

Copper(II) Acetate 184

Copper(II) Bromide 191

Copper(I) Chloride 197

Copper(II) Chloride 211

Copper(I) Iodide 219

Copper(II) Trifluoroacetate 229

Copper(II) Trifluoromethanesulfonate 230

N-Cyano-4-methyl-N-phenylbenzenesulfonamide 237

Dibenzofuran 241

Dibenzothiophene 243

1,1-Di-tert-butyl Peroxide 247

Di-tert-butyl(methyl)phosphine 252

Di-tert-butyl(methyl)phosphonium Tetrafluoroborate 258

Dichlorobis(acetonitrile) Palladium 264

Dichlorobis(triphenylphosphine)palladium(II) 280

Di-μ-chlorotetrakis[(1,2-η)-cyclooctene]diiridium 291

Di-μ-methoxobis(1,5-cyclooctadiene)diiridium(I) 292

Dimethyl Diazomalonate 296

(2S,5S)-2-(1,1-Dimethylethyl)-3-methyl-5-

(phenylmethyl)-4-imidazolidinone 306

Diphenyliodonium Hexafluorophosphate 310

Diphenyliodonium Triflate 312

Dysprosium Trifluoromethanesulfonate 315

N-fluoro-N-(phenylsulfonyl)benzenesulfonamide 319

1-Fluoro-2,4,6-trimethylpyridinium Tetrafluoroborate 330

Furan 334

Gallium(III) Trifluoromethanesulfonate (Gallium Triflate) 339

Hafnium(IV) Trifluoromethanesulfonate 343

Hypofluorous acid–acetonitrile complex 349

Indium(III) Triflate 355

Indolizine 361

Iron, Bis(pyridine)bis(2-pyridinecarboxylato-N1,O2) 363

Isoindole 366

Isoquinoline 367

Lithium t-Butoxide 371

Lithium Dichloro(1-methylethyl)-magnesate 373

Lithium Dichloro(2,2,6,6-tetramethylpiperidinato)-zincate 375

Magnesium tert-butoxide 379

Manganese(III) Acetate 380

4-Methoxypyridine N-oxide 389

6-Methoxyquinoline-N-oxide 392

2-Methylbenzothiazole 395

N-Methylimidazole 398

N-Methylindole 411

1-[[(4-Methylphenyl)sulfonyl]amino]-pyridinium

inner salt 414

Methyltrioxorhenium 415

Nitric Acid 427

4,4,4_,4_,5,5,5_,5_-Octamethyl-2,2_-bi-1,3,2-dioxaborolane 435

1,2,5-Oxadiazole 447

Oxalyl Chloride–Dimethylformamide 448

Oxazole 449

Palladium(II) Acetate 457

Palladium(II) Bromide 491

Palladium(II) Chloride 499

Palladium(π-cinnamyl) Chloride Dimer 516

Palladium Pivalate 517

Pentamethylcyclopentadienylrhodium(III) chloride dimer 519

1,10-Phenanthroline 525

1,10-Phenanthroline, 1-oxide 528

(1,10-Phenanthroline) (trifluoromethyl)

(triphenylphosphine)copper 528

Pinacolborane 529

Pivalic Acid 536

Potassium Acetate 545

Propanoic acid, 2-Diazo-, 2-methyl-1-

(1-methylethyl)propyl ester 551

Pyridazine 554

Pyridazine N-Oxide 557

Pyridine 559

Pyridine N-Oxide 566

Pyrrole 572

Quinoline 577

Ruthenium Dodecacarbonyltri Triangulo 581

Scandium Trifluoromethanesulfonate 585

Silver(I) Acetate 594

Silver(I) Carbonate 603

Silver(I) Fluoride 612

Silver(I) Nitrate 618

Silver(I) Oxide 628

Silver(I) Trifluoromethanesulfonate 636

Sulfur Trioxide–Pyridine 649

Tetrakis(triphenylphosphine)palladium(0) 651

1,2,4,5-Tetrazine 659

1H-Tetrazole 661

1,2,3-Thiadiazole 662

1,2,4-Thiadiazole 663

2H-1,2,3-Triazole 663

1,2,4-Triazole 665

Tri-tert-butylphosphine 668

Tri-tert-butylphosphonium Tetrafluoroborate 677

Tricyclohexylphosphine 686

(S)-(Trifluoromethyl)diphenylsulfonium Triflate 697

(Trifluoromethyl)tris(triphenylphosphine)-copper 701

Tris(dibenzylideneacetone)dipalladium–Chloroform 703

Tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite 709

Yttrium Trifluoromethanesulfonate 711

Zinc Isopropylsulfinate 715

Zinc Trifluoromethanesulfinate 717

List of Contributors 000

Reagent Formula Index 000

Subject Index 000

General Abbreviations

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