Key Chiral Auxiliary Applications, Second Edition is a detailed compilation of chiral auxiliary applications organized by type of transformation. Continuing from the most important and relevant auxiliaries described in its predecessor, the three-volume set Compendium of Chiral Auxiliary Applications (2001), as well as advances in the field, the book provides a vital and timely resource for chemists in the field. Each reaction class includes a series of tables and graphical abstracts of real reactions from the literature and patents to enable easy review and comparison of results. This anticipated edition is based on a screening of nearly 40,000 auxiliary reaction applications, with details supplied for the more than 13,000 selected representative entries: synthetic route, reagents, yields, diastereomeric/enantiomeric excesses, and characterization data. Updated and streamlined with more than 60% new material, Key Chiral Auxiliary Applications provides valuable guidance and reliable content for selecting the best auxiliary for a specific asymmetric synthetic transformation.
Provides a comprehensive compilation based on nearly 40,000 diverse applications of chiral auxiliaries for selecting the best synthetic route to optically pure compounds.
Contains over 60% new material with 13,000+ auxiliary applications categorized by reaction type, with reaction details and chemical and optical yields in one unique resource.

Acknowledgements xix

Foreword xxi

Preface xxiii

Abbreviations xxv

1 INTRDUCTION 1

1.1 BACKGROUND 1.1

1.2 THE CHIRAL AUXILIARY APPROACH 2

1.3 THIS COLLECTION 3

      1.3.1 Aim and scope 3

      1.3.2 Organization 4

      1.3.3 Layout 4

REFERENCES 5

SECTION A - SUBSTITUTION RELATED PROCESSES A

2 ALKYLATION AND RELATED REACTIONS 19

2.1 ALLYL AND BENZYL RELATED CARBANIONS 10

      2.1.1 Isolated derivatives - Auxiliary on the nucleophile or electrophile 10

      2.1.2 Nitrogencontaining derivatives 10

      2.1.2.1 Aminooxazolines 10

      2.1.2.2 Formamidines 11

      2.1.2.3 Allyl systems 16

      2.1.2.4 Benzyl systems 18

      2.1.3 Oxygen derivatives - allyloxy and enol ether equivalents 21

      2.1.4 Silicon-containing allyl and benzyl derivatives 22

2.2 ALLENIC ETHER TANDEM ACYLATIONCYCLIZATION 24

2.3 ALDEHYDE DERIVED NUCLEOPHILES 26

      2.3.1 Simple aldehydes 26

      2.3.1.1 a-Alkylation 26

      2.3.1.1.2 Via imine and enamine derivatives 30

      2.3.1.2 a-Hydroxylation and a-silylation 30

      2.3.1.2.1 Sequential silylation + alkylation 30

      2.3.1.3 a-Phosphinylation 31

      2.3.2 a-Alkylation of a-heterosubstituted aldehydes 32

      2.3.2.1 a-Amino derivatives 32

      2.3.2.2 a-Oxy derivatives 32

      2.3.2.3 a-Silyl derivatives - tandem alkylation + alkylation/acylation 34

      2.3.2.4 a-Thio derivatives 34

2.4 KETONE DERIVED NUCLEOPHILES 36

      2.4.1 a-Alkylation 36

      2.4.1.1Acyclic systems with auxiliary on the ketone 36

      2.4.1.2 Cyclic systems with auxiliary on the ketone 42

      2.4.1.3 a-Heteroatom substituted ketones 46

      2.4.2 Reaction with other electrophiles 54

      2.4.2.1 a-Acylationa-Aminat ion, and a-Hydroxylation 54

      2.4.2.2 a-Silylation 56

      2.4.2.3 a-Phosphinylationa-Thiolation, and a-Halogenation 58

2.5 ALDEHYDE AND KETONE ENOLATES WITH AUXILIARY-CONTAINING ELECTROPHILES 61

      2.5.1 Alkylation, acylation, and amination 61

REFERENCES 64

3 ALKYLATI NAND RELATED REACTI NS II 69

3.1 a-ALKYLATION OF CARBOXYLIC ACID DERIVED NUCLEOPHILES 71

      3.1.1 CrAcid derivatives (acetate equivalents) 71

      3.1.1.1 Creati of an a-stereocentre (sequential bisalkylation) 71

      3.1.1.2 Creation of aor y-stereocentre 71

      3.1.2 Arylacetic acid derivatives 73

      3.1.2.1 Unsubstituted phenyl ring derivatives 73

      3.1.2.2 Substituted phenyl ring derivatives 76

      3.1.2.3 Other related derivatives 80

      3.1.3 C3-Acid derivatives (propionate equivalents) 81

      3.1.3.1 Reaction with C1-chain electrophiles 81

      3.1.3.2 Reaction with Crchain electrophiles 91

      3.1.3.3 Reaction with Crchain electrophiles 95

      3.1.3.4 Reaction with C4-chain electrophiles 103

      3.1.3.5 Reaction with C5-chain electrophiles 105

      3.1.3.6 Reaction with higher order electrophiles 107

      3.1.3.7 Reaction with sundry heterocyclic-electrophiles 109

      3.1.4 Phenylpropionic acid derivatives 111

      3.1.4.1 Unsubstituted phenyl ring derivatives 111

      3.1.4.2 Phenyl ring-substituted derivatives 117

      3.1.4.3 Related derivatives 119

      3.1.5 Malanie acid and related derivatives 120

      3.1.5.1 Bisalkylation of unsubstituted derivatives 120

      3.1.5.2 Reaction of monosubstituted derivatives 121

      3.1.6 Oxo acid and related derivatives 123

      3.1.6.1 Auxiliary on the oxo 123

      3.1.6.2 Auxiliary on the acid 126

      3.1.7 Miscellaneous substituted C3-acid derivatives 129

      3.1.7.1 /3-Heteroatom substituted derivatives 129

      3.1.7.2 /3-Cycloalkyl substituted derivatives 131

      3.1.8 C4-Acid derivatives 132

      3.1.8.1 Unsubstituted butanoic acid derivatives 132

      3.1.8.2 Succinic acid and related derivatives 137

      3.1.8.3 Unsaturated and carb substituted derivatives 138

      3.1.8.4 Heteroatom substituted derivatives 144

      3.1.9 C5-Acid derivatives 147

      3.1.9.1 Unsubstituted pentanoic acid derivatives 147

      3.1.9.2 Unsaturated and carbon substituted derivatives 149

      3.1.9.3 Heteroatom substituted derivatives 152

      3.1.10 C6-Acid derivatives 154

      3.1.10.1 Unsubstituted hexanoic acid derivatives 154

      3.1.10.2 Unsaturated and carbon substituted derivatives 155

      3.1.10.3 Heteroatom substituted derivatives 157

      3.1.11 Higher order acid derivatives 158

REFERENCES 164

4 ALKYLATI NAND RELATED REACTI NS Ill 173

4.1 a-ALKYLATION OF a-HETEROATOM SUBSTITUTED ACID DERIVATIVES 174

      4.1.1 a-Amino acid derivatives 174

      4.1.1.1 Auxiliary on the acid 174

      4.1.1.2 Auxiliary on the nitrogen 191

      4.1.1.3 Auxiliary on both acid and nitrogen 197

      4.1.1.4 Auxiliary on the electrophile 231

      4.1.2 a-Oxy derivatives 232

      4.1.2.1 Glycolic acid derivatives 232

      4.1.2.2 Higher order derivatives 241

      4.1.3 3 a-Thio derivatives 243

      4.1.4 a-Sundry hetero derivatives 244

4.2 a-ALKYLATION OF CYCLIC CARBOXYLIC ACID DERIVATIVES 245

      4.2.1 Lactones 245

      4.2.2 Lactams 246

      4.2.2.1 Monofunctional systems 246

      4.2.2.2 Bicyclic lactams (y- and b-oxo acid derivatives) 247

REFERENCES 255

5 ALKYLATI N AND RELATED REACTIONS IV 263

5.1 a-ACYLATION OF ACID DERIVATIVES 264

      5.1.1 Auxiliary on the acid derivative 264

      5.1.2 Auxiliary on the acyl electrophile 270

5.2 a-AMINATION OF ACYL DERIVATIVES 271

      5.2.1 Electrophilic amino equivalents 271

      5.2.2 Nucleophilic amino equivalents (halogenation + substitution) 283

5.3 a-HYDROXYLATION OF ACID DERIVATIVES 285

5.4 a-SILYLATION a-THIOLATION , AND a-SELENATION OF ACID DERIVAT IVES 288

5.5 a-HALOGENAT ION OF ACID DERIVATIVES 289

5.6 REACTION OF PHOSPHORIC ACID DERIVATIVES WITH ELECTROPHILES 292

      5.6.1 a-Alkylation 292

      5.6.1.1 Alkyl, aralkyl, and haloalkyl derivatives 292

      5.6.1.2 a-Amino derivatives 293

      5.6.2 a-Amination and a-halogenation 296

5.7 a-ALKYLATION OF SULFONIC ACID DERIVATIVES 296

5.8 AROMATIC SUBSTITUTION 298

      5.8.1 Electrophilic 298

      5.8.1.1 Friedel-Crafts type reactions 298

      5.8.1.2 Arenechromium tricarbonyl carbanions 299

      5.8.1.3 Ortho-metallation reactions 301

      5.8.2 Nucleophilic 303

      5.8.3 Radical 306

5.9 NUCLEOPHILIC ALLYLIC SUBSTITUTION 306

5.10 MISCELLANEOUS REACTIONS 309

      5.10.1 Protonation/equilibration of auxiliary-bear ing substrates 309

      5.10.2 Radical coupling 311

      5.10.3 Sundry nucleophiles with auxiliary-bearing electrophiles 313

REFERENCES 320

SECTION B - ADDITION TO UNSATURATED SYSTEMS

6 ELECTROPHILIC RELATED ADDITION TO C=C 329

6.1 REDUCTION AND RELATED REACTIONS 330

      6.1.1 Catalytic hydrogenation 330

      6.1.1.1 Carbon substituted aB-unsaturated acyl derivatives 330

      6.1.1.2 Heteroatom substituted aunsaturated acyl derivatives 331

      6.1.1.3 Enamides 335

      6.1.1.4 Aromatic systems 336

      6.1.2 Dissolving metal reduction of aromatic systems 338

      6.1.2.1 Tandem reductive alkylation of acyl substituted aromatic systems 338

6.2 ADDITION OF HALO-CONTAINING ADDENDS 344

      6.2.1 Halogenation 344

      6.2.2 Halohydrin and related products 344

6.3 BISAMINATION 348

6.4 ADDITION OF OXY-ADDENDS 348

      6.4.1 Dihydroxylation 348

      6.4.2 Epoxidation 351

6.5 CYCLOPROPANATION 357

      6.5.1 Auxiliary on acceptor 357

      6.5.1.1 Acyclic alkenes 357

      6.5.1.2 Cycloalkenes 364

      6.5.2 Auxiliary on donor 367

      6.5.3 lntramolecular 370

      6.5.4 Tandem cyclopropanation + rearrangement 371

6.6 CYCLOPROPENATION 373

6.7 AZIRIDINATION 373

6.8 ALKOYSELENATI ON 375

6.9 RADICAL ADDITION 377

      6.9.1 Auxiliary on acceptor alkene 377

      6.9.1.1 Intermolecular 377

      6.9.1.2 lntramolecular 386

      6.9.2 Auxiliary on donor radical 387

      6.9.3 Coupling/dimerization 389

REFERENCES 390

7 CONJUGATE ADDITION I 397

7.1 AUXILIARY ON DONOR NUCLEOPHILE - SIMPLE ADDITION 398

      7.1.1 Acyl anion equivalents 398

      7.1.1.1 Formyl derivatives 398

      7.1.1.2 Higher Order derivatives 400

      7.1.2 Aldehyde-de rived en late equivalents 402

      7.1.3 Ketone-derived enolate equivalents 404

      7.1.3.1 Alkyl derivatives 404

      7.1.3.2 Aralkyl derivatives 407

      7.1.3.3 Cyclic derivatives 408

      7.1.3.4 1,3-Dicarbonyl derivatives (,B-keto esters and diketones) 414

      7.1.4 Acyl enolate equivalents 419

      7.1.4.1 Simple acyl derivatives 419

      7.1.4.2 Lactam and lactone derivatives 425

      7.1.4.3 a-Aminoacid derivatives - auxiliary on the acid 426

      7.1.4.4 a-Aminoacid derivatives - auxiliary on the nitrogen 426

      7.1.4.5 a-Amino acid derivatives - auxiliary on both the acid and nitrogen bislactims, Ni-complexes) 429

      7.1.4.6 a-Alkoxy acyl derivatives (glycolates) 438

      7.1.4.7 a-Seleno acyl derivatives 440

      7.1.5 Sulfonic ester enolates 440

      7.1.6 Phosphonate anions 441

      7.1.7 Conjugated phosphonamide -based anions 442

      7.1.8 Nitrogen nucleophiles 443

7.2 AUXILIARY ON DONOR NUCLEOPHILE - TANDEM ADDITION 446

      7.2.1 Acyl-anion equivalents conjugate addition + alkylation 446

      7.2.2 Carbonyl-based donor nucleophiles 447

      7.2.2.1 Conjugate addition + alkylation 447

      7.2.2.2 Conjugate addition + aldol reaction 449

      7.2.2.3 Others 450

      7.2.3 Acyl enolate equivalents 451

      7.2.3.1 Conjugate addition + alkylation 451

      7.2.3.2 Conjugate addition + conjugate addition 452

      7.2.4 Nitrogen nucleophiles 452

      7.2.4.1 Conjugate addition + alkylation 452

      7.2.4.2 Conjugate addition + conjugate addition and/or aldol reaction 454

      7.2.5 Conjugated phosphonamide anions - conjugate addition + alkylation 455

      7.2.6 Sulfur nucleophiles - conjugate addition + reduction 456

REFERENCES 458

8 CONJUGATE ADDITION II 463

8.1 AUXILIARY ON ACCEPTOR ap.UNSATURATED SYSTEM - SIMPLE ADDITION 464

      8.1.1 aUnsaturated aldehyde-based derivatives 464

      8.1.1.1 Addition of carbon nucleophiles 464

      8.1.1.2 Addition of alkoxy nucleophiles 466

8.1.2 ap.Unsaturated ketone-based derivatives - Addition of carbon nucleophiles 466

8.1.3 aUnsaturated acyl derivatives - addition of carbon nucleophiles 469

      8.1.3.1 Acrylic/methacrylic and related acid derivatives 469

      8.1.3.2 Crotonic and related acid derivatives 471

      8.1.3.3 Malonic and keto ester derivatives 486

      8.1.3.4 Higher order aliphatic a-p.unsaturated acyl derivatives 489

      8.1.3.5 ap.Unsaturated aromatic acyl derivatives 500

      8.1.3.6 Heteroatom substituted derivatives 519

REFERENCES 521

9 CONJUGATE ADDITION III 525

9.1 aUNSATURATED ACYL DERIVATIVES -ADDITION OF HETERONUCLEOPH ILES 526

      9.1.1 Hydride (conjugate reduction) 526

      9.1.2 Nitrogen derivatives 526

      9.1.3 Alkoxides 533

      9.1.4 Thiolates 534

      9.1.5 Phosphate anions 537

      9.1.6 Silyl anions 538

      9.1.7 Halides 539

9.2 OTHER ACTIVATED SYSTEMS 540

      9.2.1 a-Acylcyclopropenes and acylallenes 540

      9.2.2 aUnsaturated sulfoximine and sulfonic acid derivatives 540

      9.2.3 ap.Unsaturated nitro derivatives (addition/elimination) 542

      9.2.4 Activated aromatic acid derivatives 544

      9.2.5 1,4-Addition to pyridinium systems 545

      9.2.5.1 N-alkyl derivatives 545

      9.2.5.2 N-acyl derivatives 548

9.3 INTRAMOLECULAR REACTIONS 550

9.4 AUXILIARY ON aUNSATURATED SYSTEM - TANDEM ADDITION OF CARBON NUCLEOPHILES 552

      9.4.1 Carbonyl-based derivatives - Conjugate addition + alkylation 552

      9.4.2 Acyl-based derivatives 553

      9.4.2.1 Conjugate addition + alkylation 553

      9.4.2.2 Conjugate addition + halogenation 558

      9.4.2.3 Conjugate addition + conjugate addition 559

      9.4.2.4 Conjugate addition + C=N addition 560

      9.4.2.5 Conjugate addition + C=O addition 561

9.5 AUXILIARY ON ACCEPTOR aUNSATURATED SYSTEM - TANDEM ADDITION OF HETERONUCLEOPHI LES 563

      9.5.1 Conjugate addition + alkylation 563

      9.5.1.1 Hydride (reductive alkylation) 563

      9.5.1.2 Nitrogen derivatives 563

      9.5.1.3 Silyl derivatives 566

      9.5.1.4 Tin derivatives 567

      9.5.2 Conjugate addition + C=N addition 567

      9.5.3 Conjugate addition + C=O addition 568

9.6 AUILIARY ON ACCEPTOR a,-UNSATURATED SYSTEM - RADICAL ADDITION 570

9.7 NUCLEOPHILIC ADDITION TO TRANSITION-METAL ALKENE/ARENE COMPLEXES 573

      9.7.1 Auxiliary on the donor nucleophile 573

      9.7.2 Auxiliary on the acceptor transition-metal complex 574

REFERENCES 577

10 ADDITION TO C=N BONDS 581

10.1 REDUCTION OF IMINES, IMINIUM IONS, HYDRAZONES AND OXIMES 583

10.2 NUCLEOPHILIC ADDITION 585

      10.2.1 Imines - auxiliary on nitrogen 585

      10.2.1.1 Carbon-based nucleophiles 585

      10.2.1.2 Phosphite nucleophiles 598

      10.2.1.3 Tandem reactions 599

      10.2.2 Imines - auxiliary on carbon 602

      10.2.2.1 Glyoxal and glyoxylate derivatives 602

      10.2.2.2 Pyruvaldehyde derivatives 604

      10.2.3 lmines - auxiliary on nucleophile 605

      10.2.3.1 Addition of simple enolate equivalents 605

      10.2.3.2 Addition of organometallics 615

      10.2.3.3 Addition of a-heteroatom substituted enolates 616

      10.2.3.4 Addition of heteronucleophiles 620

      10.2.4 Oximes - auxiliary on oxygen 622

      10.2.5 Oximes - auxiliary on carbon 623

      10.2.6 Oximes - auxiliary on nucleophile 624

      10.2.7 lminium derivatives 624

      10.2.7.1 Intermolecular addition with auxiliary on the iminium 624

      10.2.7.2 Auxiliary on nucleophile 636

      10.2.7.3 lntramolecular addition 638

      10.2.8 Hydrazones 638

      10.2.8.1 Simple alkyl/aryl aldehyde derivatives 638

      10.2.8.2 a-Amino and a-Alkoxy substituted aldehyde derivatives 654

      10.2.8.3 aa-Heteroatom substituted hydrazones (glyoxal and pyruvaldehyde derivatives) 655

      10.2.9 Hydrazonium derivatives 659

      10.2.10 Nitrone derivatives 660

10.3 RADICAL ADDITION 663

      10.3.1 Hydrazones 663

      10.3.2 Oximes 664

10.4 UGI COUPLING 666

REFERENCES 670

11 ADDITION TO COBONDS I 675

11.1 REDUCTION 676

      11.1.1 Acetals 676

      11.1.2 a-Keto aldehydes 676

      11.1.3 1,2-Diketones 678

      11.1.4 a-Keto acid derivatives 679

      11.1.5 Aminoketones 684

      11.1.6 Ket aldehydes 685

      11.1.7 Keto acid derivatives 685

      11.1.8 Sundryketo derivatives 687

11.2 WITTIG & RELATED OLEFINATION 688

11.3 ADDITION OF ORGANOMETALLIC AND RELATED REAGENTS 693

      11.3.1 Auxiliary-bearing acceptor carbonyl derivatives 693

      11.3.1.1 Acetals 693

      11.3.1.2 a-Aminocarbonyl derivatives 693

      11.3.1.3 1,2-Dicarbonyl derivatives 694

      11.3.1.4 a-Oxo acid derivatives 708

      11.3.1.5 n-Hydroxycarbonyl derivatives 718

      11.3.1.6 1,n-Dicarbonyl derivatives 719

      11.3.1.7 Acyl carbonyl derivatives 721

      11.3.2 Auxiliary-bearing organometallic donor reagents 723

      11.3.2.1 Acyl anion equivalents (formyl, acetyl) 723

      11.3.2.2 Allylic and benzylic related derivatives 727

      11.3.2.3 Aromatic derivatives 732

      11.3.2.4 Auxiliary-bearing heteroatom donor reagents 733

      11.3.2.5 Miscellaneous 734

REFERENCES 736

12 ADDITION TO COBONDS II 741

12.1 ADDITION OF ENOLATES (ALDOL AND RELATED REACTIONS) 742

      12.1.1 Auxiliary-bearing acceptor carbonyl derivatives 742

      12.1.2 Auxiliary-beari ng enolate equivalents from carbonyl precursors 744

      12.1.2.1 Creation of a single stereocentre 744

      12.1.2.2 Creation of two stereocentres 746

      12.1.3 Auxiliary-beari ng enolate equivalents from carboxylic acid precursors 749

      12.1.3.1 Acetate equivalents 749

      12.1.3.2 Propionate equivalents 767

13 ADDITION TO C=O BONDS III 829

13.1 ADDITION OF ENOLATES (ALDOL AND RELATED REACTIONS) 830

      13.1.1 Auxiliary-bearing enolate equivalents from carboxylic acid precursors 830

      13.1.1.1 Higher order equivalents 830

      13.1.1.1.2 Creation of a two stereocentres 832

      13.1.1.1.2.1 Phenacyl and phenethyl derivatives 832

      13.1.1.1.2.2 Others 836

      13.1.1.2 af3- and {3, y-Unsaturated acyl enolate equivalents 851

      13.1.1.3 Auxiliary-bearing a-heteroacyl derivatives 863

      13.1.1.4 Homoenolate equivalents 901

13.2 TANDEM REACTIONS 903

13.3 RADICAL REACTIONS 909

      13.3.1 Addition by auxiliary-bearing donor radicals 909

      13.3.2 lntramolecular addition 911

      13.3.3 Couplir19 reactions 912

REFERENCES 915

SECTION C - PERICYCLIC AND RELATED REACTIONS

14 CYCLOADDITIONS I 925

14.1 [2+2]-CYCLOADDITIONS 926

      14.1.1 Photochemical reactions 927

      14.1.1.1 Cyclobutane formation 927

      14.1.1.2 Oxetane (Paterno-Buchi reaction) and dioxetane formation 931

      14.1.2 Reactions of ketene-based derivatives 933

      14.1.2.1 Reaction of ketenes with auxiliary-bearing alkenes 933

      14.1.2.2 Reaction of ketene acetals/thioacetals with auxiliary-bearing alkenes 934

      14.1.2.3 Reaction of ketenes with imines (Staudinger reaction) 935

      14.1.2.4 Cyclobutanone formation from keteniminium derivatives and alkenes 942

14.2 [3+2] CYCLOADDITIONS 943

      14.2.1 Photochemical reactions 943

      14.2.2 Alkyl diazo dipoles - reaction with auxilia bearing C=C dipolarophiles 944

      14.2.3 Nitrile oxide dipoles 946

      14.2.3.1 Auxiliary on the dipolarophile 946

      14.2.3.2 Auxiliary on the nitrile oxide dipole 954

      14.2.4 Nitrilimine dipoles with C=C dipolarophiles 954

      14.2.5 Nitrone dipoles 956

      14.2.5.1 Auxiliary on C=C dipolarophile 956

      14.2.5.2 Auxiliary on the nitr ne dipole 960

      14.2.6 Silyl nitronate dipoles - reaction with auxiliary-bearing C=C dipolarophiles 968

      14.2.7 Azomethine and related ylide dipoles 969

      14.2.7.1 Auxiliary on the C=C dipolarophile 969

      14.2.7.2 Auxiliary on the ylide dipole 978

      14.2.7.3 Thiocarbonyl ylides 982

      14.2.8 Sundry transition metal-mediated equivalents REFERENCES 982

15 CYCLOADDITIONS II 987

15.1 [4+2]-INTERMOLECULAR HOMO-CYCLOADDITIONS 991

(DIELS-ALDER REACTIONS) - AUXILIARY ON THE DIENOPHILE 993

      15.1.1 Acrylic acid derivatives with acyclic dienes 993

      15.1.1.1 Butadiene 993

      15.1.1.2 Monosubstituted butadienes 993

      15.1.1.3 Disubstituted butadienes 996

      15.1.2 Acrylic acid derived dienophiles with cyclic dienes 997

      15.1.2.1 Cyclopentadienes 997

      15.1.2.2 Cyclohexadienes 1006

      15.1.2.3 Heterocyclic dienes 1008

      15.1.2.4 Miscellaneous dienes 1010

      15.1.3 Methacrylic acid derived dienophiles 1010

      15.1.4 Other a or -substituted acrylic-related dienophiles 1012

      15.1.5 Allene derived dienophiles 1014

      15.1.6 Crotonic acid derived dienophiles 1015

      15.1.6.1 Acyclic dienes 1015

      15.1.6.2 Cyclic dienes 1018

      15.1.7 Cinnamic and related aromatic acid derived dienophiles 1022

      15.1.8 Fumaric and maleic acid derived dienophiles 1025

      15.1.8.1 Acyclic dienes 1025

      15.1.8.2 Cyclic dienes 1027

      15.1.9 Miscellaneous acyl-derived dienophiles 1030

      15.1.10 Heteroatom substituted non-acyienophiles (allyl amines/ethers) 1032

      15.1.11 Cyclic d1enophiles 1034

      15.1.12 Tandem processes 1038

15.2 [4+2]-INTERMOLECULAR HOMO-CYCLOADDITIONS (DIELS-ALDER REACTIONS)-AUXILIARY ON THE DIENE 1040

      15.2.1 Acyclic dienes 1040

      15.2.1.1 2,4-Dienoic acid derivatives 1040

      15.2.1.2 N-Functionalized dienes (enamine) 1041

      15.2.1.3 N,O-Functionalized dienes (enamine/enol ehter) 1044

      15.2.1.4 O-Functionalized dienes (enol ehter) 1045

      15.2.1.5 O,O-Functionalized dienes (ketene acetal/enol ether) 1047

      15.2.1.6 S,O-Functionalized dienes (sulfinyl/enol ether) 1049

      15.2.2 Cyclic dienes 1050

15.3 [4+2]-INTRAMOLECULAR HOMO-CYCLOADDITIONS (DIELS-ALDER REACTIONS) 1059

15.4 [4+2]-HETERO-CYCLOADDITIONS (HETERO-DIELS-ALDER REACTIONS) 1063

      15.4.1 Auxiliary on dienophile 1063

      15.4.1.1 Nin heterodiene 1063

      15.4.1.2 0 in heterodiene 1064

      15.4.1.3 S in heterodiene 1067

      15.4.1.4 N/0 in heterodiene 1068

      15.4.1.5 N/S in heterodiene 1071

      15.4.1.6 N/N/0 in heterodiene 1071

      15.4.2 Auxiliary on heterodienophile 1071

      15.4.2.1 N in heterodienophile 1071

      15.4.2.2 0 in heterodienophile 1073

      15.4.2.3 S in heterodienophile 1074

      15.4.2.4 N/0 in heterodienophile 1075

      15.4.2.5 N/S in heterodienophile 1080

      15.4.3 Auxiliary on diene 1080

      15.4.3.1 Nin heterodienophile 1080

      15.4.3.2 0 in heterodienophile 1081

      15.4.3.3 S in heterodienophile 1082

      15.4.3.4 NIN in heterodienophile 1085

      15.4.3.5 N/0 in heterodienophile 1085

      15.4.3.6 0/0 in heterodienophile 1086

15.4.4 Auxiliary on heterodiene 1086

      15.4.4.1 Nin heterodiene 1087

      15.4.4.2 0 in heterodiene 1088

      15.4.4.3 S in heterodiene 1088

      15.4.4.4 N/ 0 in heterodiene 1088

15.5 (4+3] CYCLOADDITIONS 1088

      15.5.1 lntermolecular 1092

      15.5.2 lntramolecular 1093

15.6 (6+2] AND (6+4] CYCLOADDITIONS 1093

15.7 ELECTROCYCLIC REACTIONS 1097

REFERENCES 1097

16 REARRANGEMENTS REACTIONS 1107

16.1 (2,3]-SIGMATROPIC VARIANTS 1108

      16.1.1 Wittig rearrangement 1108

      16.1.1.1 Tandem Wittig rearrangement-aldol 1112

      16.1.1.2 Aza-Wittig rearrangement 1112

      16.1.2 Meisenheimer rearrangement 1113

      16.1.3 Sommelet-Hauser and related rearrangements 1114

      16.1.4 Others 1115

16.2 [3,3]-SIGMATROPIC VARIANTS 1118

      16.2.1 Carroll rearrangement 1118

      16.2.2 Claisen rearrangement 1118

      16.2.2.1 Johnson-Claisen rearrangement 1120

      16.2.2.2 Eschenrnoser-Claisen and Ficini-Claisen rearrangements 1120

      16.2.2.3 Overman and related Claisen rearrangements 1122

      16.2.3 Hetero-Claisen rearrangements 1124

      16.2.3.1 Aza-Claisen rearrangement 1124

      16.2.3.2 Thio-Claisen rearrangement 1125

      16.2.4 Oxy-Cope/siloxy-Cope rearrangement 1128

      16.2.5 Other related variants 1130

16.3 SUNDRY REARRANGEMENTS 1131

      16.3.1 Photochemical processes 1131

      16.3.1.1 Deconjugation 1131

      16.3.1.2 Rearrangement of auxiliary salts 1133

      16.3.1.3 Other variants 1136

      16.3.2 Sundry others 1138

16.4 ENE REACTIONS 1139

      16.4.1 C=C enophiles 1139

      16.4.2 C=N enophiles 1140

      16.4.3 C=O enophiles 1140

      16.4.4 N=N enophiles (Azaene reaction) 1142

      16.4.5 N=O enophiles 1143

      16.4.6 N=S en phiIes 1144

      16.4.7 O=O enophiles (Schenck reaction) 1145

REFERENCES 1147

SECTION D - MISCELLANEOUS PROCESSES

17A KINETIC RESOLUTION-RELATED PROCESSES 1153

17.1 SIMPLE KINETIC RESOLUTION 1154

17.2 CRYSTALLIZATION INDUCED DYNAMIC RESOLUTION 1155

17.3 DYNAMIC KINETIC RESOLUTION OF AUXILIARY-BEARING ELECTROPHILES 1156

      17.3.1 Carbon nucleophiles 1156

      17.3.2 Nitrogen nucleophiles 1157

      17.3.2.1 Amino and amino/amido derivatives 1157

      17.3.2.2 Diamino derivatives 1164

      17.3.3 Oxygen nucleophiles 1166

      17.3.3.1 Hydroxy derivatives 1166

      17.3.3.2 Hydroxyamino derivatives 1168

      17.3.4 Sulfur nucleophiles 1169

17.4 DERACEMIZATION/DYNAMIC KINETIC RESOLUTION VIA ACYLATION-TYPE REACTIONS 1170

      17.4.1 Auxiliary on the nucleophile 1170

      17.4.1.1 Nitrogen nucleophiles 1170

      17.4.1.2 Oxygen nucleophiles 1173

      17.4.1.3 Hydroxyamino and hydroxyamido nucleophiles 1180

      17.4.2 Auxiliary on the acyl-related electrophile 1186

      17.4.2.1 Carbon nucleophiles 1186

      17.4.2.2 Nitrogen nucleophiles 1188

      17.4.2.3 Oxygen nucleophiles 1188

17.5 DESYMMETRATION OF MESO COMPOUNDS 1191

      17.5.1 Cyclic ketones 1191

      17.5.2 Diols 1193

      17.5.2.1 Acyclic 1,n-diols 1193

      17.5.2.2 Cyclic 1,n-diols 1195

      17.5.3 Diacid/anhydride derivatives 1197

      17.5.3.1 1,1-Dicarboxylic derivatives (Malonic acid-related systems) 1197

      17.5.3.2 1,2-Dicarboxylic derivatives (Succinic acid and related systems) 1198

      17.5.3.3 1,3-Dicarboxylic derivatives (Glutaric acid and related systems) 1202

      17.5.3.4 1,4- and 1,5-Dicarboxylic derivatives 1205

      17.5.4 1,2-Disulfones 1206

      17.5.5 Dienes 1206

REFERENCES 1208

17B MISCELLANEOUS REACTIONS 1211

17.6 TRANSITION-METAL CONTROLLED REACTIONS 1212

      17.6.1 Carbene insertion reactions 1212

      17.6.1.1 C-H lnsertion 1212

      17.6.1.2 0-H Insertion 1214

      17.6.1.3 Si-H Insertion 1215

      17.6.1.4 C-C Insertion 1216

      17.6.2 Coupling reactions 1217

      17.6.2.1 Coupling of allylic/benzylic derivatives 1217

      17.6.2.2 Coupling of aryl derivatives 1219

      17.6.2.3 Other sundry couplings 1220

      17.6.3 Cyclization reactions 1223

      17.6.3.1 Heck reactions 1223

      17.6.3.2 Pauson-Khand cyclization 1223

      17.6.3.3 Other sundry cyclizations 1228

      17.6.4 Organometallic complex formation 1235

17.7 PHOTOCHEMICAL CYCLIZATIONS 1236

17.8 MISCELLANEOUS CYCLIZATIONS 1238

17.9 SULFOXIDE PREPARATION FROM SULFIDES 1239

17.10 ELIMINATION REACTIONS 1240

17.11 BIO-TRANSFORMATIONS 1241

REFERENCES 1242

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