Reagents for Silicon-Mediated Organic Synthesis

ISBN-13: 9780470710234 / Angielski / Twarda / 2011 / 854 str.

Philip L. Fuchs

Opis

Over the last three decades the importance of organosilicon chemistry has greatly increased because it has opened a number of new synthetic strategies. Silicon reagents are usually low-cost, versatile and allow a wide range of reactions. This is the first Handbook to compile essential Silicon containing reagents and makes use of the leading reagent database e-EROS. Another hot volume in the series Handbooks of Reagents for Organic Synthesis, this is a must-have resource for all synthetic chemists working in drug development and medicinal chemistry. For the selection the Editor focussed on three key synthetic approaches with the greatest impact: 1. Use of silicon as a 'temporary tether' by unifying a reactive pair of functional groups and taking advantage of their template-biased intramolecular cyclization. 2. The specific use of the silane functionality as a hetero t-butyl group, often colloquially referred to as the use of silicon as a 'fat proton'. 3. The use of the Brook rearrangement as an 'anion relay stratagem'. A new feature in this Handbook is the reagent finder, an alphabetically organized lookup table arranged by organic functionality and specific structure of the silicon atom to which it is bound.

Spis treści

Preface xiii

Introduction xv

Reagent Finder Table xxiii

Short Note on InChIs and InChIKeys xxxi

3–Acetoxy–2–trimethylsilylmethyl–1–propene 1

Allyl(2–chloroethyl)dimethylsilane 9

Allyl Trichlorosilane 10

Allyltrimethylsilane 14

Allyltrimethylsilylzinc Chloride 24

Ammonium Hexafluorosilicate 25

Azidotrimethylsilane 26

Benzene, [[Difluoro(trimethylsilyl)methyl]seleno] 33

Benzene, [[Difluoro(trimethylsilyl)methyl]thio]– 36

Benzene, [[(1E)–2–(Trimethylsilyl)ethenyl]seleno] 39

Benzene, [[(1E)–2–trimethylsilyl)ethenyl]sulfonyl]– 42

2,1–Benzoxasilole, 1,3–Dihydro–1,1–dimethyl– 43

N–Benzyl–N–(methoxymethyl)–Ntrimethylsilylmethylamine 44

1,2–Bis(t–butyldimethylsilyl)hydrazine 46

1,2–Bis(chlorodimethylsilyl)ethane 48

1,4–Bis(dimethylamino)–1,1,4,4–tetramethyldisilethylene 50

Bis(1–methoxy–2–methyl–1–propenyloxy)dimethylsilane 51

Bis(methylthio)(trimethylsilyl)methane 52

[Bis(2–pyridyldimethylsilyl)methyl]lithium 54

1,3–Bis(triisopropylsilyl)propyne 56

N,O–Bis(trimethylsilyl)acetamide 58

(1E,3E)–1,4–Bis(trimethylsilyl)–1,3–butadiene 73

Bis(ß–trimethylsilylethanesulfonyl)imide 74

N,O–Bis(trimethylsilyl)hydroxylamine 75

Bis[(trimethylsilyl)methyl]zinc 76

Bis(trimethylsilyl) Peroxide 79

Bis(trimethylsilyl) Selenide 82

Bis(trimethylsilyl) Sulfide 83

Bromomagnesium Hexamethyldisilazide 85

(Bromomethyl)chlorodimethylsilane 85

Bromotrimethylsilane 92

(E)–1–Bromo–4–trimethylsilyl–1–buten–3–yne 100

(Z)–2–Bromo–1–(trimethylsilyloxy)ethylene 105

2–Bromo–3–trimethylsilyl–1–propene 106

(1–Bromovinyl)trimethylsilane 109

t–Butyldimethylchlorosilane 110

t–Butyldimethylsilyl Cyanide 120

(t–Butyldimethylsilyl)diphenylphosphine 121

2–t–Butyldimethylsilyl–1,3–dithiane 122

O–(t–Butyldimethylsilyl)hydroxylamine 124

N–(t–Butyldimethylsilyl)–N–methyltrifluoroacetamide 125

t–Butyldimethylsilyl Trifluoromethanesulfonate 127

t–Butyldiphenylchlorosilane 135

1–t–Butylthio–1–t–butyldimethyl–silyloxyethylene 138

1–t–Butylthio–1–t–butyldimethylsilyloxypropene 141

t–Butyl Trimethylsilylacetate 147

3–Butyn–2–ol, 4–(Trimethylsilyl)– 148

Chlorodiisopropylsilane 151

Chlorodimethylsilane 156

Chlorodimethylvinylsilane 157

Chlorodiphenylsilane 162

(Chloromethyl)dimethylphenylsilane 162

(E)–(3–Chloro–1–methyl–1–propenyl)–trimethylsilane 166

1–Chloro–1–methylsiletane 166

Chlorotrimethylsilane 170

Chlorotriphenylsilane 182

Cyanotrimethylsilane 184

Diazo(trimethylsilyl)methyllithium 191

(Dibromomethyl)trimethylsilane 197

Di–t–butylchlorosilane 198

Di–t–butyldichlorosilane 201

trans–1,1–Di–t–butyl–2,3–dimethylsilirane 207

Di–t–butylsilyl Bis(trifluoromethanesulfonate) 209

Dichlorodiisopropylsilane 222

Dichlorodimethylsilane 228

1,3–Dichloro–1,1,3,3–tetraisopropyldisiloxane 230

1,1–Dichloro–2,2,2–trimethyl–1–phenyldisilane 233

Dicyanodimethylsilane 234

1,2–Diethoxy–1,2–bis(trimethylsilyloxy)ethylene 235

N,N–Diethylaminodimethylsilane 237

Diethyl[dimethyl(phenyl)silyl]aluminum 237

Diiododimethylsilane 238

Diisopropyl Chlorosilane, Polymer–supported 240

Diisopropylsilyl Bis(trifluoromethanesulfonate) 241

Dilithium Cyanobis(dimethylphenylsilyl)–cuprate 248

(a,a–Dimethylallyl)trimethylsilane 252

(2–Dimethylaminomethylphenyl)phenylsilane 253

Dimethyl(phenyl)silane 254

Dimethylphenylsilyllithium 255

1,1–Dimethylsilacyclobutane 261

Dimethylthexylsilyl Chloride 263

Dimethylthexylsilyl Trifluoromethanesulfonate 265

1,3,2–Dioxaborolane, 2–(Dimethylphenylsilyl)–4,4,5,5– tetramethyl–, 1,3,2–Dioxaborolane, 4,4,5,5–Tetramethyl– 2–(methyldiphenylsilyl)–, 1,3,2–Dioxaborolane, 4,4,5,5– Tetramethyl–2–(triphenylsilyl)– 270

Diphenyldifluorosilane 276

Disilane, 1,1,1,2,2,2–hexamethyl– 278

1–Ethoxy–1–(trimethylsilyloxy)cyclopropane 285

Ethoxy(trimethylsilyl)acetylene 289

Ethyl Lithio(trimethylsilyl)acetate 293

Ethyl (Methyldiphenylsilyl)acetate 295

Ethyl 2–(Methyldiphenylsilyl)propanoate 296

Ethyl Trimethylsilylacetate 297

Fluorosilicic Acid 301

Formamide, N–N,bis(trimethylsilyl)– 302

Hexachlorodisilane 309

Hexamethylcyclotrisiloxane 310

Hexamethyldisiloxane 313

Hexamethyldisilazane 317

(Iodoethynyl)trimethylsilane 321

(Iodomethyl)trimethylsilane 323

Iodotrimethylsilane 325

(E)–1–Iodo–3–trimethylsilyl–2–butene 336

3–Iodo–2–trimethylsilylmethyl–1–propene 338

Isocyanatotrimethylsilane 339

Ketene t–Butyldimethylsilyl Methyl Acetal 341

3–Lithio–1–triisopropylsilyl–1–propyne 347

Lithium N–Benzyltrimethylsilylamide 349

Lithium Bis[dimethyl(phenyl)silyl]cuprate 350

Lithium Cyano(dimethylphenylsilyl)cuprate 353

Lithium Hexamethyldisilazide 356

Methanamine, 1,1–Bis(trimethylsilyl) 369

Methanesulfonamide, 1,1,1–Trifluoro–N[(trifluoromethyl)sulfonyl]–N(trimethylsilyl)– 372

(Methoxymethyl)bis(trimethylsilyl)amine 374

1–Methoxy–2–methyl–1–(trimethylsilyloxy)propene 376

N–Methyl–N,O–bis(trimethylsilyl)–hydroxylamine 380

Methyldiphenylchlorosilane 381

(Methylthio)trimethylsilane 388

Methyltrichlorosilane 389

Methyl Trichlorosilyl Ketene Acetal (1) 393

Methyl 2–Trimethylsilylacrylate 396

1–Methyl–1–(trimethylsilyl)allene 397

2–Methyl–2–(trimethylsilyloxy)–3–pentanone 400

PDMS Thimbles 403

Phenylsilane Cesium Fluoride 408

(2–Phenylsulfonylethyl)trimethylsilane 409

Phenylthiobis(trimethylsilyl)methane 411

(Phenylthiomethyl)trimethylsilane 412

(Phenylthio)trimethylsilane 414

1–(Phenylthio)–1–(trimethylsilyl)cyclopropane 418

1–Phenylthio–1–trimethylsilylethylene 419

2–(Phenylthio)–2–(trimethylsilyl)propane 420

Phenyl Trimethylsilyl Selenide 421

Phosphine, Tris(trimethylsilyl)– 422

Polymethylhydrosiloxane 427

Potassium Hexamethyldisilazide 432

(+)–9–(1S,2S–Pseudoephedrinyl)–(10R)–(trimethylsilyl)– 9–borabicyclo[3.3.2]decane 453

2–Pyridyldimethylsilane 457

Silane, 1,1–(Chloromethylene)bis[1,1,1]–trimethyl– 461

Silane, Chlorotri–2–propen–1–yl– 463

Silane, 1,1–(1–Propene–1,3–diyl)bis[1,1,1–trimethyl–(E)

Silane, 1,1–(1–Propene–1,3–diyl)bis[1,1,1–trimethyl–(Z)

Silane, 1,1–(1–Propene–1,3–diyl)bis[1,1,1– trimethyl–(E + Z) 464

Sodium Hexamethyldisilazide 468

Tetrabutylammonium Difluorotriphenylsilicate 479

2,4,6,8–Tetraethenyl–2,4,6,8–tetramethylcyclotetrasiloxane 484

3–Tetrahydropyranyloxy–1–trimethylsilyl–1–propyne 487

1,1,3,3–Tetramethyldisilazane 488

1,1,2,2–Tetraphenyldisilane 490

Trialkylsilyl Cyanide, Polymer–supported 494

Tribenzylchlorosilane 496

Tri(t–butoxy)silanethiol 497

(E)–1–Tri–n–butylstannyl–2–trimethylsilylethylene 499

Trichloroiodosilane 500

Triethoxysilane 501

Triethylsilane 506

Triethylsilyl Hydrotrioxide 514

3–Triethylsilyloxy–1,4–pentadiene 515

(a–Triethylsilyl)propionaldehyde Cyclohexylimine 516

Triethylsilyl Trifluoromethanesulfonate 517

Trimethylsilyl Trifluoromethanesulfonate 518

Trifluoromethanesulfonic Acid, Chlorobis (1,1–Dimethylethyl)silyl Ester 537

Trifluoromethyltrimethylsilane 539

Triisopropylsilanethiol 546

(Triisopropylsilyl)acetylene 550

Triisopropylsilyl Chloride 554

Triisopropylsilylethynyl Triflone 558

Triisopropylsilyl Trifluoromethanesulfonate 559

Trimethylsilylacetic Acid 562

Trimethylsilylacetone 563

Trimethylsilylacetonitrile 564

Trimethylsilylacetylene 569

(Trimethylsilyl)allene 580

Trimethylsilylallyllithium 582

(E)–1–Trimethylsilyl–1,3–butadiene 585

3–Trimethylsilyl–3–buten–2–one 586

9–[1–(Trimethylsilyl)–2(E)–butenyl] –9–borabicyclo[3.3.1]nonane 588

Trimethylsilylcopper 589

Trimethylsilyldiazomethane 590

Trimethylsilyldiethylamine 598

2–Trimethylsilyl–1,3–dithiane 604

2–(Trimethylsilyl)ethanesulfonamide 609

ß–Trimethylsilylethanesulfonyl Chloride 611

[N–(2–(Trimethylsilyl)ethanesulfonyl)–imino]phenyliodane 617

2–(Trimethylsilyl)ethanethiol 618

2–(Trimethylsilyl)ethanol 622

2–(Trimethylsilyl)ethoxycarbonylimidazole 627

2–(Trimethylsilyl)ethoxymethyl Chloride 628

[2–(Trimethylsilyl)ethoxymethyl]triphenylphosphonium Chloride 633

2–(Trimethylsilyl)ethyl Chloroformate 634

2–(Trimethylsilyl)ethyl 3–Nitro–1H–1,2,4–triazole–1–carboxylate 636

(Trimethylsilyl)ethynylcopper(I) 637

Trimethylsilyl Fluorosulfonyldifluoroacetate 638

N–(Trimethylsilyl)imidazole 640

Trimethylsilylketene 645

Trimethylsilyllithium 650

Trimethylsilyl Methanenitronate 653

1–Trimethylsilyl–1–methoxyallene 656

Trimethylsilylmethyl Azide 657

1–[(Trimethylsilyl)methyl]–1H–benzotriazole 658

2–Trimethylsilylmethyl–1,3–butadiene 660

3–[(Trimethylsilyl)methyl]–3–butenoic Acid Methyl Ester 662

Trimethylsilylmethyllithium 664

Trimethylsilylmethylmagnesium Chloride 666

Trimethylsilylmethylpotassium 674

2–Trimethylsilylmethyl–2–propen–1–ol 675

1–Trimethylsilyloxy–1,3–butadiene 677

2–Trimethylsilyloxy–1,3–butadiene 681

2–Trimethylsilyloxyfuran 684

(Z)–2–(Trimethylsilyloxy)vinyllithium 693

5–Trimethylsilyl–1,3–pentadiene 695

2–(Trimethylsilyl)phenyl Triflate 697

Trimethylsilylpotassium 700

2–Trimethylsilyl–1,3–propanediol 701

3–Trimethylsilyl–2–propen–1–yl Acetate 703

3–Trimethylsilyl–1–propyne 704

3–Trimethylsilyl–2–propynylcopper(I) 711

2–(Trimethylsilyl)thiazole 712

Trimethylsilyltributylstannane 719

3–Trimethylsilyl–3–trimethylsilyloxy–1–propene 723

(E)–1–Trimethylsilyl–2–trimethylstannylethylene 724

(Trimethylsilyl)vinylketene 725

1–(Trimethylsilyl)vinyllithium 726

(E)–2–(Trimethylsilyl)vinyllithium 729

1–(Trimethylsilyl)vinylmagnesium Bromide Copper(I) Iodide 730

Trimethyl{2–[(tributylstannyl)methyl]–2–propenyl}silane 731

Triphenylsilane 733

Tris(dimethylamino)sulfonium Difluorotrimethylsilicate 739

Tris(trimethylsilyl)aluminum 745

Tris(trimethylsilyl)methane 746

Tris(trimethylsilyl)silane 747

Vinyltrimethylsilane 755

List of Contributors 763

Reagent Formula Index 779

Subject Index 785 ???

Blurb

Reagents for Silicon–Mediated Organic Synthesis

Silicon reagents are usually low–cost, versatile and allow a wide range of reactions. For the selection the Editor focused on three key synthetic approaches with the greatest impact:

• Use of silicon as a temporary tether by unifying a reactive pair of functional groups and taking advantage of their template–biased intramolecular cyclization
• The specific use if the silane functionality as a hetro t–butyl group, often colloquially referred to as the use of silicon as a fat proton .
• The use of the Brook rearrangement as an anion relay stratagem . A new feature in this Handbook is the reagent finder, and alphabetically organized lookup table arranged by organic functionality and specific structure of the silicon atom to which it is bound.

All the information compiled in this volume is also available in electronic format on Wiley Online Library. The electronicEncyclopedia of Reagents for Organic Synthesis (e–EROS) includes all the reagents described in this volume plus many more reagents of other types and for other uses. e–EROS allows for text and structure search and has many new and updated entries added every year.