Handbook of Reagents for Organic Synthesis

André B. Charette received his B.Sc. in 1983 from the Université de Montréal. He then moved south of the border to the University of Rochester to continue his graduate studies. Under the supervision of Robert K. Boeckman Jr., he completed the total synthesis of the ionophore calcimycin, which earned him the degrees of M.Sc. (1985) and Ph.D. (1987). Following an NSERC postdoctoral fellowship at Harvard University with D. A. Evans, he began his academic career at the Université Laval (Quebec City) in 1989. In 1992, he joined the Université de Montréal, where he has been promoted to the rank of Full Professor since 1998. With a record of close to 200 publications and numerous invited lectures throughout the world, Prof. Charette has achieved worldwide recognition in his field. His research lies primarily in the development of new methods for the stereoselective synthesis of organic compounds and natural products. Among his recent honors are the CSC Alfred Bader Award (2009), the Prix Marie Victorin of the Government of Quebec (2008), and an ACS Arthur C. Cope Award (2007).

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