Additions to C-X ?-Bonds

Opis

Volume 2 deals mainly with the addition reactions of delocalized carbanions (enolates) and their synthetic relatives (metalloenamines, enol ethers, allyl organometallics) with carbonyl compounds, imines and iminium ions. Major emphasis is placed on C-C bond-forming reactions such as the aldol and Mannich reactions. Acylation reactions are also included in this volume. Several topics that have not previously been reviewed are covered, including the use of enzymatic aldol reactions in synthesis and the Passerini-Ugi reactions.

Spis treści

Front Cover 2
Additions to C—X π- Bonds 5
Copyright Page 6
Table of Contents 7
Preface 9
Contributors to Volume 2 11
Abbreviations 15
Contents of All Volumes 19

Front Cover 2
Additions to C—X π- Bonds 5
Copyright Page 6
Table of Contents 7
Preface 9
Contributors to Volume 2 11
Abbreviations 15
Contents of All Volumes 19
Part I: Uncatalyzed Additions ofNucleophilic Alkenes to C=X 553
- Chapter 1.1. Allyl Organometallics 27
  - 1.1.1 INTRODUCTION 27
  - 1.1.2 SIMPLE DIASTEREOSELECTION 29
  - 1.1.3 RELATIVE DIASTEREOSELECTION 50
  - 1.1.4 SINGLE ASYMMETRIC SYNTHESIS: REACTIONS OF ACHIRAL ALDEHYDES AND CHIRAL ALLYL ORGANOMETALLICS 59
  - 1.1.5 DOUBLE ASYMMETRIC SYNTHESIS: REACTIONS OF CHIRAL C = X ELECTROPHILES AND CHIRAL ALLYL ORGANOMETALLICS 66
  - 1.1.6 SUMMARY 72
  - 1.1.7 ADDENDUM 73
  - 1.1.8 REFERENCES 75
- Chapter 1.2. Heteroatom-stabilized Allylic Anions 81
  - 1.2.1 SYNTHETIC UTILITY 81
  - 1.2.2 BORON-SUBSTITUTED ALLYLIC ANIONS 82
  - 1.2.3 SILICON-SUBSTITUTED ALLYLIC ANIONS 83
  - 1.2.4 NITROGEN-SUBSTITUTED ALLYLIC ANIONS 86
  - 1.2.5 PHOSPHINE-SUBSTITUTED ALLYLIC ANIONS 90
  - 1.2.6 OXYGEN-SUBSTITUTED ALLYLIC ANIONS 92
  - 1.2.7 SULFUR-SUBSTITUTED ALLYLIC ANIONS 97
  - 1.2.8 SELENIUM-SUBSTITUTED ALLYLIC ANIONS 102
  - 1.2.9 HALOGEN-SUBSTITUTED ALLYLIC ANIONS 103
  - 1.2.11 REFERENCES 104
  - 1.2.10 ADDENDUM 104
- Chapter 1.3. Propargyl and Allenyl Organometallics 107
  - 1.3.2 PREPARATION OF PROPARGYL AND ALLENYL ORGANOMETALLICS 107
  - 1.3.3 STRUCTURE AND PHYSICAL PROPERTIES 107
  - 1.3.1 INTRODUCTION 107
  - 1.3.4 REGIOSELECTIVE REACTIONS 108
  - 1.3.5 DIASTEREOSELECTIVE REACTIONS 117
  - 1.3.6 ENANTIOSELECTIVE REACTIONS 122
  - 1.3.7 REFERENCES 123
- Chapter 1.4. Formation of Enolates 125
  - 1.4.1 INTRODUCTION 125
  - 1.4.2 ALKALI METAL ENOLATES 126
  - 1.4.3 MAGNESIUM ENOLATES 136
  - 1.4.4 BORON ENOLATES 137
  - 1.4.5 ALUMINUM ENOLATES 140
  - 1.4.6 TIN ENOLATES 142
  - 1.4.7 TITANIUM ENOLATES 143
  - 1.4.8 ZIRCONIUM ENOLATES 145
  - 1.4.9 COPPER ENOLATES AND ENOLATES FROM CUPRATES 145
  - 1.4.10 ZINC ENOLATES 148
  - 1.4.11 OTHER TRANSITION METAL ENOLATES 151
  - 1.4.12 REFERENCES 154
- Chapter 1.5. The Aldol Reaction: Acid and General Base Catalysis 159
  - 1.5.1 INTRODUCTION 159
  - 1.5.2 BACKGROUND 160
  - 1.5.3 REVERSIBILITY OF THE ALDOL REACTION 160
  - 1.5.5 SELF-REACTIONS OF ALDEHYDES 162
  - 1.5.4 OVERVIEW: REACTIONS UNDER PROTIC CONDITIONS 162
  - 1.5.6 MIXED REACTIONS OF ALDEHYDES 165
  - 1.5.7 SELF-REACTIONS OF KETONES 166
  - 1.5.8 MDCED REACTIONS OF KETONES 168
  - 1.5.9 REACTIONS OF KETONES WITH ALDEHYDES 168
  - 1.5.10 INTRAMOLECULAR ALDOL REACTIONS 182
  - 1.5.11 REFERENCES 202
- Chapter 1.6. The Aldol Reaction: Group I and Group II Enolates 207
  - 1.6.1 INTRODUCTION 207
  - 1.6.2 FORMATION AND ALDOL REACTIONS OF REGIO-DEFINED ENOLATES 208
  - 1.6.3 SIMPLE DIASTEREOSELECTION 216
  - 1.6.4 DIASTEREOFACIAL SELECTIVITY 243
  - 1.6.5 EQUILIBRATION; THERMODYNAMIC CONTROL 260
  - 1.6.6 REFERENCES 261
- Chapter 1.7. The Aldol Reaction: Group III Enolates 265
  - 1.7.1 INTRODUCTION 265
  - 1.7.2 BORON-MEDIATED ALDOL REACTION 266
  - 1.7.3 ALUMINUM-MEDIATED ALDOL REACTION 294
  - 1.7.4 REFERENCES 299
- Chapter 1.8. Zinc Enolates: the Reformatsky and Blaise Reactions 303
  - 1.8.1 INTRODUCTION 303
  - 1.8.2 NATURE OF THE REFORMATSKY REAGENT 304
  - 1.8.3 REACTION WITH ALDEHYDE AND KETONE SUBSTRATES 307
  - 1.8.4 REACTION WITH IMINES 320
  - 1.8.5 REACTION WITH ACYLATING AGENTS 322
  - 1.8.6 REFERENCES 324
- Chapter 1.9. The Aldol Reaction: Transition Metal Enolates 327
  - 1.9.1 INTRODUCTION 327
  - 1.9.2 ALDOL REACTIONS OF η1-O-BOUND METAL ENOLATES 328
  - 1.9.3 ALDOL REACTIONS OF η1 -C-BOUND METAL ENOLATES AND η3-METAL ENOLATES 338
  - 1.9.4 ALDOL REACTIONS OF METAL ENOLATES OF ACYL-TRANSITION METAL COMPLEXES 340
  - 1.9.5 OTHER ASYMMETRIC ALDOL REACTIONS INVOLVING TRANSITION METALS 343
  - 1.9.6 ADDENDUM 344
  - 1.9.7 REFERENCES 344
- Chapter 1.10. The Henry (Nitroaldol) Reaction 347
  - 1.10.1 INTRODUCTION 347
  - 1.10.2 GENERAL CONSIDERATIONS ON THE NITROALDOL REACTION AND ITS UTILITY IN ORGANIC SYNTHESIS 348
  - 1.10.3 CLASSICAL NITROALDOL PROCEDURES AND THEIR LIMITATIONS 351
  - 1.10.4 NITROALDOL REACTIONS WITH SILYL NITRONATES AND WITH α,α DOUBLY DEPROTONATED NITROALKANES 361
  - 1.10.5 ADDENDUM 364
  - 1.10.6 REFERENCES 365
- Chapter 1.11. The Knoevenagel Reaction 367
  - 1.11.1 INTRODUCTION 367
  - 1.11.2 GENERAL ASPECTS 369
  - 1.11.3 SCOPE AND LIMITATION 380
  - 1.11.4 SEQUENTIAL REACTIONS 395
  - 1.11.5 SYNTHETIC APPLICATIONS 401
  - 1.11.7 REFERENCES 414
  - 1.11.6 SYNTHETIC ALTERNATIVES 414
- Chapter 1.12. The Perkin Reaction 421
  - 1.12.1 INTRODUCTION 421
  - 1.12.2 MECHANISTIC CONSIDERATIONS 422
  - 1.12.3 REACTION SCOPE 425
  - 1.12.4 ERLENMEYER AZALACTONE SYNTHESIS 428
  - 1.12.5 REFERENCES 433
- Chapter 1.13. Darzens Glycidic Ester Condensation 435
  - 1.13.1 INTRODUCTION 435
  - 1.13.2 GENERAL AND MECHANISTIC CONSIDERATIONS 437
  - 1.13.3 CONDENSATIONS EMPLOYING ANIONS STABILIZED BY SUBSTITUENTS OTHER THAN SIMPLE ESTERS 441
  - 1.13.4 MISCELLANEOUS MODIFICATIONS 453
  - 1.13.5 PREPARATION OF AZIRIDINES 454
  - 1.13.6 CONDENSATIONS UNDER MULTIPHASE CONDITIONS 455
  - 1.13.7 ASYMMETRIC VARIANTS OF THE DARZENS CONDENSATION 461
  - 1.13.8 REFERENCES 464
- Chapter 1.14. Metal Homoenolates 467
  - 1.14.1 INTRODUCTION 467
  - 1.14.2 ELIMINATION 469
  - 1.14.3 FORMATION AND CLEAVAGE OF CYCLOPROPANE RINGS 469
  - 1.14.5 CARBONYL ADDITION 471
  - 1.14.4 SYMMETRICAL COUPLING 471
  - 1.14.6 CONJUGATE ADDITION 474
  - 1.14.7 SUBSTITUTION REACTIONS 475
  - 1.14.8 CARBON YLATION 477
  - 1.14.9 SYNTHETIC APPLICATIONS 477
  - 1.14.10 REFERENCES 479
- Chapter 1.15. Use of Enzymatic Aldol Reactions in Synthesis 481
  - 1.15.1 INTRODUCTION 481
  - 1.15.2 ENZYMES AS CATALYSTS 482
  - 1.15.3 D-FRUCTOSE-1,6-DIPHOSPHATE ALDOLASE 482
  - 1.15.4 N-ACETYLNEURAMINIC ACID ALDOLASE 489
  - 1.15.5 TRANSKETOLASE 490
  - 1.15.6 KDO SYNTHETASE 491
  - 1.15.7 DAHP SYNTHETASE 492
  - 1.15.8 CONCLUSION AND FUTURE PERSPECTIVES 492
  - 1.15.9 REFERENCES 497
- Chapter 1.16. Metalloenamines 501
  - 1.16.1 INTRODUCTION 501
  - 1.16.2 DIRECTED ALDOL REACTIONS OF IMINE ANIONS 503
  - 1.16.3 ADDITION REACTIONS OF HETEROATOM-STABILIZED IMINE ANIONS 508
  - 1.16.4 ADDITION REACTIONS OF METALLATED OXIME DERIVATIVES 512
  - 1.16.5 ADDITIONS OF METALLATED DERIVATIVES OF IMIDATES 514
  - 1.16.6 OTHER METALLATED AZOMETHINE DERI VATI VES 521
  - 1.16.7 ADDITIONS OF METALLATED BIS-LACTIM ETHERS OF 2,5-DDCETOPIPERAZINES 524
  - 1.16.8 REFERENCES 527
- Chapter 1.17. Hydrazone Anions 529
  - 1.17.1 INTRODUCTION 529
  - 1.17.2 PREPARATION OF HYDRAZONES FROM ALDEHYDES AND KETONES 530
  - 1.17.3 FORMATION OF AZAALLYL METAL REAGENTS FROM HYDRAZONES 532
  - 1.17.4 STRUCTURES OF AZAALLYL METAL REAGENTS DERIVED FROM HYDR AZONES 533
  - 1.17.5 REGIOCHEMICAL AND STEREOCHEMICAL CONTROL IN HYDRAZONE DEPROTONATION 535
  - 1.17.6 1,2-ADDITIONS TO ALDEHYDES AND KETONES 537
  - 1.17.7 1,2-ADDITIONS TO CARBOXYLIC ACID DERIVATIVES 542
  - 1.17.8 1,4-CON JUG ATE ADDITIONS TO α,β-UNSATURATED CARBONYL DERIVATIVES 543
  - 1.17.9 HETEROCYCLE SYNTHESES VIA 1,2- AND 1,4-ADDITIONS OF HYDRAZONE ANIONS TO CARBONYL COMPOUNDS AND α,β-UNSATURATED CARBONYL C 546
  - 1.17.10 HYDRAZONE ANIONS AS ACYL ANION EQUIVALENTS 549
  - 1.17.11 CLEAVAGE OF HYDRAZONES TO REGENERATE CARBONYL GROUPS 549
  - 1.17.12 REFERENCES 551
- Part II: Catalyzed Additions ofNucleophilic Alkenes to C=X 553
  - Chapter 2.1. The Prins and Carbonyl Ene Reactions 553
    - 2.1.1 INTRODUCTION 553
    - 2.1.2 INTERMOLECULAR REACTIONS 554
    - 2.1.3 INTRAMOLECULAR REACTIONS 566
    - 2.1.4 THIOCARBONYL COMPOUNDS 581
    - 2.1.5 ADDENDUM 582
    - 2.1.6 REFERENCES 584
  - Chapter 2.2. Allylsilanes, Allylstannanes and Related Systems 589
    - 2.2.1 INTRODUCTION 589
    - 2.2.2 MECHANISM 590
    - 2.2.3 ALDEHYDES AND KETONES 593
    - 2.2.4 ACETALS AND KETALS 602
    - 2.2.5 OTHER SUBSTRATES AT THE OXIDATION LEVEL OF ALDEHYDES AND KETONES 606
    - 2.2.6 SYNTHESES OF THE SILANES AND STANNANES 608
    - 2.2.7 REFERENCES 616
  - Chapter 2.3. Formation and Addition Reactions of Enol Ethers 621
    - 2.3.1 INTRODUCTION 621
    - 2.3.2 PREPARATION OF ENOL ETHERS 622
    - 2.3.3 REACTIONS WITH C—X π-BONDS AND EQUIVALENTS 637
    - 2.3.5 REFERENCES 651
    - 2.3.4 CONCLUSIONS 651
  - Chapter 2.4. Asymmetric Synthesis with Enol Ethers 655
    - 2.4.1 INTRODUCTION 655
    - 2.4.2 PROCHIRAL NUCLEOPHILES AND ELECTROPHILES (SIMPLE STEREOSELECTION) 656
    - 2.4.3 CHIRAL NUCLEOPHILES 662
    - 2.4.4 CHIRAL ELECTROPHILES 665
    - 2.4.5 CHIRAL NUCLEOPHILES AND ELECTROPHILES 678
    - 2.4.6 CHIRAL LEWIS ACIDS 680
    - 2.4.7 ADDENDUM 681
    - 2.4.8 REFERENCES 683
  - Chapter 2.5. Reactions of Activated Dienes with Aldehydes 687
    - 2.5.1 INTRODUCTION 688
    - 2.5.2 MECHANISM 690
    - 2.5.3 DIASTEREOFACIAL SELECTIVITY 703
    - 2.5.4 METHODS TO CONTROL ABSOLUTE STEREOCHEMISTRY 706
    - 2.5.5 APPLICATIONS IN ORGANIC SYNTHESIS 715
    - 2.5.6 REFERENCES 731
  - Part III: Addition-Elimination Reactions (Acylations) 733
    - Chapter 3.1. The Aliphatic Friedel–Crafts Reaction 733
      - 3.1.1 INTRODUCTION 733
      - 3.1.2 GENERAL ASPECTS OF ALIPHATIC FRIEDEL-CRAFTS ACYLATIONS 734
      - 3.1.3 ACYLATIONS OF ALKENES 735
      - 3.1.4 ACYLATIONS OF SILANES 738
      - 3.1.5 ACYLATIONS OF CONJUGATED DIENES 746
      - 3.1.6 ACYLATION OF ALKYNES 749
      - 3.1.7 ACYLATION OF TIN SUBSTRATES 752
      - 3.1.8 ACYLATIONS OF ALK ANES 753
      - 3.1.9 ALIPHATIC FORMYLATION 754
      - 3.1.10 REFERENCES 755
    - Chapter 3.2. The Bimolecular Aromatic Friedel–Crafts Reaction 759
      - 3.2.1 INTRODUCTION 759
      - 3.2.2 MECHANISMS 760
      - 3.2.3 REAGENT SYSTEMS 761
      - 3.2.4 ACYLATION REACTIONS 765
      - 3.2.5 FRIES REACTIONS 771
      - 3.2.6 REACTIONS USING NITRILES — THE HOUBEN-HOESCH SYNTHESIS 773
      - 3.2.7 VILSMEIER AND RELATED KETONE SYNTHESES 774
      - 3.2.8 PALLADIUM-MEDIATED KETONE SYNTHESES 775
      - 3.2.9 GATTERMANN AND RELATED FORMYLATION REACTIONS 775
      - 3.2.10 REFERENCES 776
    - Chapter 3.3. The Intramolecular Aromatic Friedel–Crafts Reaction 779
      - 3.3.1 INTRODUCTION 779
      - 3.3.2 ELECTRON DENSITY CONSIDERATIONS 780
      - 3.3.3 THE SIZE OF THE RING 781
      - 3.3.5 REFERENCES 792
      - 3.3.4 CONCLUSION 792
    - Chapter 3.4. The Reimer–Tiemann Reaction 795
      - 3.4.2 THE NORMAL REACTION 795
      - 3.4.1 INTRODUCTION 795
      - 3.4.3 SCOPE AND LIMITATIONS 796
      - 3.4.4 RECENT DEVELOPMENTS 797
      - 3.4.5 THE ABNORMAL REIMER-TIEMANN REACTION 799
      - 3.4.6 THE MECHANISM OF THE REACTION 800
      - 3.4.7 CONCLUSIONS 801
      - 3.4.8 REFERENCES 801
    - Chapter 3.5. The Vilsmeier–Haack Reaction 803
      - 3.5.1 INTRODUCTION 803
      - 3.5.3 REACTIONS OF AROMATIC COMPOUNDS WITH CHLOROMETHYLENIMINIUM SALTS 805
      - 3.5.2 FORMATION OF CHLOROMETHYLENEIMINIUM SALTS 805
      - 3.5.4 REACTIONS OF ALKENE DERIVATIVES WITH CHLOROMETHYLENEIMINIUM SALTS 807
      - 3.5.5 REACTIONS OF ACTIVATED METHYL AND METHYLENE GROUPS WITH CHLOROMETHYLENEIMINIUM SALTS 811
      - 3.5.6 REACTIONS OF NONCARBON NUCLEOPHILES WITH CHLOROMETHYLENE IMINIUM SALTS 816
      - 3.5.7 MISCELLANEOUS REACTIONS OF CHLOROMETHYLENEIMINIUM SALTS 817
      - 3.5.8 REFERENCES 818
    - Chapter 3.6. Acylation of Esters, Ketones and Nitriles 821
      - 3.6.1 INTRODUCTION 822
      - 3.6.2 MECHANISM 823
      - 3.6.3 THE ACYLATION OF ESTERS 825
      - 3.6.4 ACYLATION OF KETONES BY ESTERS AND OTHER ACID DERIVATIVES 855
      - 3.6.5 STEREOCHEMISTRY 872
      - 3.6.6 THORPE AND THORPE-ZIEGLER REACTIONS 874
      - 3.6.7 TANDEM REACTIONS 878
      - 3.6.8 RETRO-REACTIONS 881
      - 3.6.9 CONCLUSIONS 883
      - 3.6.10 REFERENCES 885
    - Chapter 3.7. The Eschenmoser Coupling Reaction 891
      - 3.7.1 INTRODUCTION 891
      - 3.7.2 MECHANISM 893
      - 3.7.3 MODIFICATIONS AND EXTENSIONS 899
      - 3.7.4 APPLICATIONS IN TOTAL SYNTHESIS 902
      - 3.7.5 REFERENCES 918
    - Part IV: Additions of Nucleophilic Alkenes to C=NR and C=NR2+ 919
      - Chapter 4.1. The Bimolecular Aliphatic Mannich and Related Reactions 919
        
        4.1.1 BACKGROUND — THE CLASSICAL MANNICH REACTION 919
        
        4.1.2 USE OF PREFORMED IMINIUM SALTS 924
        
        4.1.3 USE OF IMINES 941
        
        4.1.4 ADDENDUM 974
        
        4.1.5 REFERENCES 974
      - Chapter 4.2. The Bimolecular Aromatic Mannich Reaction 979
        
        4.2.1 INTRODUCTION 979
        
        4.2.2 MECHANISMS 980
        
        4.2.3 REACTIONS USING SECONDARY AMINES 982
        
        4.2.4 REACTIONS USING PRIMARY AMINES 994
        
        4.2.5 REACTIONS USING IMINES 996
        
        4.2.6 AMIDO ALKYLATION REACTIONS 997
        
        4.2.7 REFERENCES 998
      - Chapter 4.3. Reactions of Allyl and Propargyl/Allenic Organometallics with Imines and Iminium Ions 1001
        
        4.3.1 INTRODUCTION 1001
        
        4.3.2 REACTIONS WITH IMINES 1006
        
        4.3.3 REACTIONS WITH N-HETEROSUBSTITUTED IMINES 1020
        
        4.3.4 REACTIONS WITH IMINIUM SALTS 1026
        
        4.3.5 REACTIONS WITH CEM-AMINO ETHERS 1029
        
        4.3.6 REFERENCES 1032
      - Chapter 4.4. The Intramolecular Mannich and Related Reactions 1033
        
        4.4.1 INTRODUCTION 1033
        
        4.4.2 CYCLIZATION WITH ð-NUCLEOPHILES 1035
        
        4.4.3 ELECTRON TRANSFER INDUCED PHOTOCYCLIZATIONS 1063
        
        4.4.4 MOLECULAR REARRANGEMENTS TERMINATED BY MANNICH CYCLIZATIONS 1066
        
        4.4.5 REFERENCES 1070
      - Chapter 4.5. Additions to N-Acyliminium Ions 1073
        
        4.5.1 INTRODUCTION 1073
        
        4.5.2 GENERAL ASPECTS 1074
        
        4.5.3 ENDOCYCLIC IMINIUM IONS WITH THE N-ACYL GROUP IN THE RING 1083
        
        4.5.4 ENDOCYCLIC IMINIUM IONS WITH THE N-ACYL GROUP OUTSIDE THE RING 1092
        
        4.5.5 ACYCLIC N-ACYLIMINIUM IONS 1096
        
        4.5.6 C,N-DIACYLIMINIUM IONS (GLYCINE CATION EQUIVALENTS) 1100
        
        4.5.7 REFERENCES 1106
      - Chapter 4.6. The Passerini and Ugi Reactions 1109
        
        4.6.1 INTRODUCTION AND BRIEF HISTORY OF ISOCYANIDE CHEMISTRY 1109
        
        4.6.2 THE PASSERINI REACTION AND RELATED REACTIONS 1110
        
        4.6.3 THE UGI REACTION 1113

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