Handbook of Reagents for Organic Synthesis

Preface xi

Introduction xiii

Catalyst Finder xv

Recent Review Articles and Monographs xix

Short Note on InChIs and InChIKeys xxi

4-Acetamido-2,2,6,6-tetramethyl-1-piperidinyloxyl 1

4-Acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium Tetrafluoroborate 2

2[1]-Amino-[1,1[1]-binaphthalen]-2-ol 13

(9R)-9-Amino-9-deoxyquinidine 16

9(S)-Amino-9-deoxyquinine 24

(1R,2S)-1-Amino-2,3-dihydro-1H-inden-2-ol 35

(2S,4S)-2-(Anilinomethyl)-1-ethyl-4-hydroxypyrrolidine 50

(S)-2-(Anilinomethyl)pyrrolidine 51

9-Azabicyclo[3.3.1]nonane-N-oxyl 59

Benzoyl trimethylsilane 61

Benzyl 1,3-Butadiene-1-carbamate 66

3-Benzyl-5-(2-hydroxyethyl)-4-methyl-1,3-thiazolium Chloride 69

(S)-5-Benzyl-2-mesityl-6,6-dimethyl-6,8-dihydro-5H-[1,2,4]triazolo[3,4-C][1,4]-oxazin-2-ium Tetrafluoroborate 72

3-Benzyl-4-methyl-1,3-thiazolium Chloride 75

cis-4-Benzyloxy-a, a-bis-(3,5-dimethylphenyl)-L-prolinol (2S,4R)- 76

N-Benzylquininium Chloride 78

3-Benzylthiazolium Bromide 85

Benzyltriethylammonium Chloride 86

Bicyclo[2.2.1]heptan-2-one,7,7- Dimethyl-1-(1S,3S,4R)-2-thiabicyclo-[2.2.1]hept-3-yl-, (1S,4R) 88

[1,1[1]-Binaphthalene]-2,2[1]-diol, 3,3[1]-Bis[3,5-bis(trifluoromethyl)phenyl]-, (1R)- 95

N,N[1]-(1S)-[1,1[1]-Binaphthalene]-2,2[1]-diy lbis-(2S,2[1]S)-pyrrolidine-2-carboxamide 98

(R)-1,1[1]-Bi-2,2[1]-naphthol 101

1,1[1]-Binaphthyl-2,2[1]-disulfonic Acid 124

1,1[1]-Binaphthyl-2,2[1]-diyl Hydrogen Phosphate 129

N,N[1]-Bis[3,5-bis(trifluoromethyl)-phenyl]thiourea 133

1-[3,5-Bis(tert-butyl)phenyl]octahydro-3,6,6-trimethylcyclopenta[b]phosphole 137

1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene 139

1,3-Bis(2,6-diisopropylphenyl)imidazolidinium Chloride 146

1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene 149

(-)-(4R,5R)-4,5-Bis[hydroxy(diphenyl)-methyl]-2, 2-dimethyl-1,3-dioxolane(TADDOL) 152

(2S,5S)-2-(Bis(4-methoxyphenyl)((trimethylsilyl)oxy) methyl)-5-(4-methoxy-3,5-dimethylphenyl)pyrrolidine 161

(3R,5R,8R)- 3,8-Bis(1-methylethyl)-2,2,7,7-tetrakis(4-methylphenyl)-1,4,6,9-tetraaza-5¿5-phosphaspiro[4,4] non-5-ene, Hydrochloride salt (1:1) 162

1,2-Bis(phenylsulfonyl)ethylene 163

3,3[1]-Bis(trifluoromethanesulfonyl)-2,2[1]-dihydroxy-1,1[1]-binaphthalene 172

1-[Bis(trifluoromethanesulfonyl)methyl]-2,3,4,5,6-pentafluorobenzene 174

3-[[3,5-Bis(trifluoromethyl)phenyl]-amino]-4-[[(1R,2R)-2-(dimethylamino)-cyclohexyl]amino]-3-cyclobutene-1,2-dione 180

N-[3,5-Bis(trifluoromethyl)phenyl]-N[1]-(9R)-cinchonan-9-yl-thiourea 183

N-[3,5-Bis(trifluoromethyl)phenyl]-N[1]-[(1R,2R)-2-(dimethylamino)cyclohexyl]-thiourea 186

1-[3,5-Bis(trifluoromethyl)phenyl]-3-{(2S)-3,3-dimethyl-1-[(triphenylphosphoranylidene)amino] butan-2-yl}thiourea 189

2-[Bis[3,5-bis(trifluoromethyl)phenyl][(trimethylsilyl) oxy]methyl]pyrrolidine 192

(1R)-3,3[1]-Bis(2,4,6-trimethylphenyl)-[1,1[1]-binaphthalene]-2,2[1]-dicarboxylic acid 199

Bromamine-T 202

Bromonitromethane 205

tert-Butyl 2-(tert-butyldimethylsilyl)-2-oxoacetate 210

(S)-5-((tert-Butyldimethylsilyloxy)-diphenylmethyl)-2-phenyl-6,7-dihydro-5H-pyrrolo[2,1-c][1,2,4]triazol-2-ium Tetrafluoroborate 1a (and Related Reagents) 214

Chloramine-T 219

Cinchonanium, 1-(9-Anthracenylmethyl)-9-(propen-1-yloxy)-, Bromide(1:1), (8a,9R) 227

1,2-Cyclohexanediamine, N1,N2-Bis[4-(1-pyrrolidinyl)-2-quinolinyl]-, (1R,2R)- 235

1,4-Diazabicyclo[2.2.2]octane 241

1,3-Di-tert-butylimidazol-2-ylidene 247

Diethyl 1,4-Dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate 254

Diethyl Oxomalonate 261

1,3-Dihydro-1,3-bis(tricyclo[3.3.1.13,7]dec-1-yl)-2H-imidazol-2-ylidene 270

1,3-Dihydro-4,5-dimethyl-1,3-bis(1-methylethyl)-2H-imidazol-2-ylidene 273

4,5-Dihydro-4-phenyl-3H-dinaphtho[2,1-c:1[1],2[1]-e]phosphepin 277

2,3-Dihydro-2-phenylimidazo[2,1-b]benzothiazole 280

6,7-Dihydro-2-phenyl-5-(phenylmethyl)-5Hpyrrolo[2,1-c]-1,2,4-triazolium Chloride 286

(R)-2,2[1]-Dihydroxy-3,3[1]diphenyl-1,1[1]-binaphthyl 301

1,3-Dimesityl-4,5-dihydroimidazol-2-ylidene 304

1,3-Dimesityl-1H-imidazolium Salts and 1,3-Dimesitylimidazolylidene 306

4-Dimethylaminopyridine 309

2,2-Dimethyl-1,3-dioxan-5-one 315

Dimethyldioxirane 320

(11bR)-4-(1,1-Dimethylethyl)-4,5-dihydro-3Hdinaphtho[2,1-c:1[1],2[1]- e]phosphepin 327

[4S-(4a,5a)]-1-(1,3-Dimethyl-2-oxido-4,5-diphenyl-1,3,2-diazaphospholidine-2-yl)piperidine 330

(1R,2S,4R,5S)-2,5-Dimethyl-7-phenyl-7-phosphabicyclo[2.2.1]heptane 334

1,4-Dimethyl-1H-1,2,4-triazol-4-ium Iodide 335

(11bR)-Dinaphtho[2,1-d:1[1],2[1]-f][1,3,2]dioxaphosphepin,2,6-Bis[3,5-bis (trifluoromethyl)phenyl]-4-hydroxy-,

4-Oxide 339

(11bR)-Dinaphtho[2,1-d:1[1],2[1]-f][1,3,2]dioxaphosphepin,4-Hydroxy-2,6-di-2-naphthalenyl-, 4-Oxide 343

Dinaphtho[2,1-d:1[1],2[1]-f][1,3,2]dioxaphosphepin,4-Hydroxy-2,6-diphenyl-,4-Oxide, (11bR)-(Family of Reagents) 345

5,6-Dioxaspiro[2.4]heptane-4,7-dione 351

2,2[1]-Diphenyl-[3,3[1]-biphenanthrene]-4,4[1]- diol (VAPOL) and 3,3[1]-Diphenyl-[2,2[1]- binaphthrene]-1,1[1]-diol(VANOL) 353

a, a-Diphenyl-2-pyrrolidinemethanol 365

Dispiro[2H-pyran-2,4[1]-[4H-5,6,8b]-triazaacenaphthylene-7[1](5[1]H),2[1][1]-[2H]- pyran], 1[1],2[1],2[1]a,3,3[1],3[1][1], 4,4[1][1],5,5[1][1],6,6[1][1],8[1],8[1]a-tetradecahydro-1[1],2[1]-dimethoxy-6, 6[1][1]-dimethyl-, monohydrochloride,(1[1]S,2R,2[1]S,2[1][1]R,2[1]aS,6S,6[1][1]S,8[1]aS)- 372

N-[(4-Dodecylphenyl)sulfonyl]-2-pyrrolidinecarboxamide(Hua Cat) 373

Dodecyl 4-[[[(2S)-2-pyrrolidinylcarbonyl]-amino]sulfonyl]benzoate(Hua Cat II) 376

(11bR)-4-Hydroxy-2,6-bis[2,4,6-tris-(1-methylethyl)phenyl]-dinaphtho[2,1-d:1[1],2[1]-F][1,3,2]dioxaphosphepin-4-oxide,[(R)-TRIP] & (11bS)-4-Hydroxy-2,6-bis[2,4,6-tris(1-methylethyl)phenyl]- dinaphtho[2,1-d: 1[1],2[1]-f][1,3,2]dioxaphosphepin-4-oxide, [(S)-TRIP] 379

N-[(1S)-1-(Hydroxydiphenylmethyl)-3-methylbutyl]-2-pyrrolidinecarboxamide 393

trans-4-Hydroxy-l-proline 395

(4aR,9aS)-4-Hydroxy-4,4a,9,9a-tetrahydroindeno[2,1-b][1,4]oxazin-3(2H)-one 399

1H-Imidazolium, 1,3-Bis[2,6-bis-(1-methylethyl)phenyl],tetrafluoroborate(1-) 400

Iron(2+), tris(2,2[1]-bipyridine-N,N[1])-,Dibromide,(OC-6-11) 403

ß-Isocupreidine (ß-ICD) 406

1-Mesityl-3,4-dimethyl-4H-1,2,4-triazol-1-ium Tetrafluoroborate 411

9-Mesityl-10-methylacridinium Perchlorate 413

6[1]-Methoxy-(8S,9R)-cinchonan-9-yl N-tertbutoxycarbonyl-2-pyrrolidinecarboxylate 417

1-Methyl-2-azaadamantane N-Oxyl 420

(S)-1-Methyl-2-[(dihydroisoindol-2-yl)methyl]pyrrolidine 421

2-Methyltetrahydrofuran 422

Methyl(trifluoromethyl)dioxirane 428

Methyl Vinyl Ketone 438

d-2-Naphthylalanine, N,N[1]- [[(2S, 5S)-1-(4-pyridinyl)-2,5-pyrrolidinediyl]dicarbonyl]bis-, 3,3[1] - Dioctyl Ester1 and l-2-Naphthylalanine, N,N[1]-[[(2S,5S)-1-(4-pyridinyl)-2,5-pyrrolidinediyl]dicarbonyl]bis-, 3,3[1]-Dioctyl Ester 449

Nitroethane 451

4-Nitropyridine N-oxide 460

(2S)-N-(2,3,4,5,6-Pentafluorophenyl)-2-pyrrolidinecarboxamide 465

1,5-Pentanediamine, N,N[1]-Bis[(11bR)-3,5-dihydro-3,5-dimethyl-4-oxido-4H-dinaphtho[2,1-d:1[1],2[1]-f ]-[1,3,2]diazaphosphepin-4-yl]-N,N[1]-dimethyl 466

2-Phenyl-6,10b-dihydro-4H,5aH-5-oxa-3,10c-diaza-2-azonia-cyclopenta[c] fluorene tetrafluoroborate; 2-Pentafluorophenyl-6,10b-dihydro-4H, 5aH-5-oxa-3,10c-diaza-2-azoniacyclopenta[c]fluorine tetrafluoroborate; 6,7-Dihydro-2-phenyl-5-(phenylmethyl)-5H-pyrrolo[2,1-c]-1,2,4-triazolium chloride 474

(8a,9R)-(8[1][1]a,9[1][1]R)-1,1[1][1]-[1,3-Phenylenebis(methylene)]bis[9-hydroxy-cinchonanium]Dibromide and (9S)-(9[1][1]S)-1,1[1][1]-[1,3-Phenylenebis(methylene)]bis[9-hydroxy-cinchonanium]Dibromide 486

2-(Phenylmethoxy)acetaldehyde 489

(S)-Proline 494

(2S)-2-Pyrrolidinemethanol-a,a-bis(3,5-dimethylphenyl)and (2R)-2-Pyrrolidinemethanol-a, a-bis(3,5-dimethylphenyl) 517

1-(2-Pyrrolidinylmethyl)pyrrolidine 520

4-(1-Pyrrolidinyl)pyridine 525

5H-Pyrrolo[2,1-c]-1,2,4-triazolium, 7-Fluoro-6,7-dihydro-5-(1-methylethyl)-2-(2,3,4,5,6-pentafluorophenyl)-, (5R,7R)-, Tetrafluoroborate(1-) 528

Quinine 531

3-Quinuclidinol 547

Ruthenium (II), Tris(2,2[1]-bipyrazine-¿N1, ¿N1[1]),1(OC-6-11)- 551

Ruthenium(II), Tris(2,2[1]-bipyridine-¿N1,¿N1[1])-,(OC-6-11)- 554

Ruthenium(II), Tris(1,10-phenanthroline-¿N1,¿N10)-,(OC-6-11)- 559

4,4[1]-Spirobi[4H-dinaphth[2,1-c:1[1],2[1]-e]-azepinium],3,3[1],5,5[1]-tetrahydro- 2,6-bis(3,4,5-trifluorophenyl), bromide 561

Spiro[6H-1,3-dioxolo[4,5-c]pyran-6,5[1]-oxazolidine]-3[1]-carboxylic acid, tetrahydro-2,2-dimethyl-2[1],7-dioxo-, 2-methyl-2-propyl ester, (3aR, 5[1]S, 7aR)- 567

Squaramide 571

Tetrachlorosilane 575

2,3,5,6-Tetrahydro-2,6-bis(phenylmethyl)-1H-imidazo[1,2-a] imidazole 582

2,2,6,6-Tetramethylpiperidin-1-oxyl 583

(S)-2-(5-1H-Tetrazolyl)pyrrolidine and (R)-2-(5-1H-Tetrazolyl)pyrrolidine 595

1,2,4-Triazolo[4,3-a]pyridinium, 5,6,7,8-tetrahydro-2-(2,3,4,5,6-pentafluorophenyl)-, Tetrafluoroborate 603

Triflimide 604

N-[4-(Trifluoromethyl)benzyl]-cinchoninium Bromide 612

3-(2,4,6-Trimethylphenyl)-1-methyl-1Hbenzo[d]imidazol-3-ium Iodide 614

(5S)-2,2,3-Trimethyl-5-(phenylmethyl)-4-imidazolidinone 616

1,5,7-Trimethyl-7-(5,6,7,8-tetrahydronaphth[2,3-d ]oxazol-2-yl)-3-azabicyclo-[3.3.1]nonan-2-one 621

2-Triphenylmethylpyrrolidine 624

Tris[(trifluoromethyl)sulfonyl]methane and Related Salts 625

l-Tryptophan, N,N[1]-[[(2S,5S)-1-(4-pyridinyl)-2,5-pyrrolidinediyl]-dicarbonyl]bis-, 3,3[1]-dioctyl Ester 628

Urea, N-[3,5-Bis(trifluoromethyl)phenyl]-N[1]-[(8a,9S)-6[1]-methoxycinchonan-9-yl]-; Urea, N-[3,5-Bis(trifluoromethyl)phenyl]-N[1]-(9R)-cinchonan-9-yl- 633

List of Contributors 639

Reagent Formula Index 655