Applications of Domino Transformations in Organic Synthesis, Volume 2 (eBook)
528 Seiten
Thieme (Verlag)
978-3-13-221171-1 (ISBN)
The rapid pace of evolution in domino, or cascade-based transformations has revolutionized the practice of chemical synthesis for the creation of natural products, designed molecules, and pharmaceuticals.
'Science of Synthesis: Applications of Domino Transformations in Organic Synthesis' explores the topic thoroughly and systematically, serving as the basis for practical applications and future research. The 2-volume set presents the cutting-edge in terms of design, strategy, and experimental procedures, leading to multiple events being accomplished within a single reaction vessel. The content is organized by the core type of reaction used to initiate the event, be it a pericyclic reaction, a metal-mediated transformation, radical chemistry, or an acid-induced cascade among many others.
Volume 2 covers pericyclic reactions (Diels-Alder, sigmatropic shifts, ene reactions), dearomatizations, and additions to C-O/C-N multiple bonds.
Science of Synthesis Applications of Domino Transformations in Organic Synthesis 2 1
Title Page 7
Copyright 8
Preface 9
Science of Synthesis Reference Library 11
Volume Editor's Preface 13
Abstracts 15
Applications of Domino Transformations in Organic Synthesis 2 21
Table of Contents 23
2.1 Pericyclic Reactions 31
2.1.1 The Diels–Alder Cycloaddition Reaction in the Context of Domino Processes 31
2.1.1.1 Cascades Not Initiated by Diels–Alder Reaction 32
2.1.1.1.1 Cascades Generating a Diene 32
2.1.1.1.1.1 Ionic Generation of a Diene 32
2.1.1.1.1.1.1 Through Wessely Oxidation of Phenols 32
2.1.1.1.1.1.2 Through Ionic Cyclization 36
2.1.1.1.1.1.3 Through Deprotonation of an Alkene 37
2.1.1.1.1.1.4 Through Elimination Reactions 38
2.1.1.1.1.1.5 Through Allylation 42
2.1.1.1.1.2 Pericyclic Generation of a Diene 42
2.1.1.1.1.2.1 Through Electrocyclization 43
2.1.1.1.1.2.1.1 Through Benzocyclobutene Ring Opening 43
2.1.1.1.1.2.1.2 Through Electrocyclic Ring Closure 44
2.1.1.1.1.2.2 Through Cycloaddition or Retrocycloaddition 47
2.1.1.1.1.2.3 Through Sigmatropic Reactions 48
2.1.1.1.1.3 Photochemical Generation of a Diene 49
2.1.1.1.1.4 Metal-Mediated Generation of a Diene 50
2.1.1.1.2 Cascades Generating a Dienophile 52
2.1.1.1.2.1 Ionic Generation of a Dienophile 52
2.1.1.1.2.1.1 Through Himbert Cycloadditions 52
2.1.1.1.2.1.2 Through Benzyne Formation 53
2.1.1.1.2.1.3 Through Wessely Oxidation 54
2.1.1.1.2.2 Pericyclic Generation of a Dienophile 57
2.1.1.1.2.2.1 Through Cycloaddition/Retrocycloaddition 57
2.1.1.1.2.2.2 Through Sigmatropic Rearrangement 57
2.1.1.1.2.2.3 Through Electrocyclization 59
2.1.1.1.3 Proximity-Induced Diels–Alder Reactions 59
2.1.1.2 Diels–Alder as the Initiator of a Cascade 61
2.1.1.2.1 Pericyclic Reactions Occurring in the Wake of a Diels–Alder Reaction 61
2.1.1.2.1.1 Cascades Featuring Diels–Alder/Diels–Alder Processes 61
2.1.1.2.1.2 Cascades Featuring Diels–Alder/Retro-Diels–Alder Processes 63
2.1.1.2.1.3 [4 + 2] Cycloaddition with Subsequent Desaturation 66
2.1.1.2.2 Diels–Alder Reactions with Concomitant Ionic Structural Rearrangements 66
2.1.1.2.2.1 Pairings of Diels–Alder Reactions with Structural Fragmentations 67
2.1.1.2.2.2 Combining a Diels–Alder Reaction with Ionic Cyclization 70
2.1.1.3 Conclusions 73
2.1.2 Domino Reactions Including [2 + 2], [3 + 2], or [5 + 2] Cycloadditions 77
2.1.2.1 Domino [2 + 2] Cycloadditions 77
2.1.2.1.1 Cycloaddition of an Enaminone and ß-Diketone with Fragmentation 78
2.1.2.1.2 Cycloaddition of Ynolate Anions Followed by Dieckmann Condensation/Michael Reaction 78
2.1.2.1.3 Cycloaddition Cascade Involving Benzyne–Enamide Cycloaddition or a Fischer Carbene Complex 80
2.1.2.1.4 Cycloadditions with Rearrangement 81
2.1.2.1.4.1 Cycloaddition of an Azatriene Followed by Cope Rearrangement 81
2.1.2.1.4.2 Cycloaddition of a Propargylic Ether and Propargylic Thioether Followed by [3,3]-Sigmatropic Rearrangement 82
2.1.2.1.4.3 [3,3]-Sigmatropic Rearrangement of Propargylic Ester and Propargylic Acetate Followed by Cycloaddition 83
2.1.2.1.4.4 Cycloaddition of a Ketene Followed by Allylic Rearrangement 84
2.1.2.1.4.5 Allyl Migration in Ynamides Followed by Cycloaddition 85
2.1.2.1.4.6 1,3-Migration in Propargyl Benzoates Followed by Cycloaddition 86
2.1.2.2 Domino [3 + 2] Cycloadditions 87
2.1.2.2.1 Cycloadditions with Nitrones, Nitronates, and Nitrile Oxides 87
2.1.2.2.1.1 Reaction To Give a Nitrone Followed by Cycloaddition 88
2.1.2.2.1.2 Cycloaddition with a Nitrone and Subsequent Reaction 92
2.1.2.2.1.3 Reaction To Give a Nitronate Followed by Cycloaddition 93
2.1.2.2.1.4 Reaction To Give a Nitrile Oxide Followed by Cycloaddition 94
2.1.2.2.1.5 Cycloaddition with a Nitrile Oxide and Subsequent Reaction 95
2.1.2.2.2 Cycloadditions with Carbonyl Ylides 96
2.1.2.2.2.1 Reaction of an a-Diazo Compound To Give a Carbonyl Ylide Followed by Cycloaddition 96
2.1.2.2.2.2 Reaction of an Alkyne To Give a Carbonyl Ylide Followed by Cycloaddition 102
2.1.2.2.3 Cycloadditions with Azomethine Ylides 103
2.1.2.2.4 Cycloadditions with Azomethine Imines 110
2.1.2.2.5 Cycloadditions with Azides 111
2.1.2.2.5.1 Reaction To Give an Azido-Substituted Alkyne Followed by Cycloaddition 111
2.1.2.2.5.2 Cycloaddition of an Azide and Subsequent Reaction 113
2.1.2.3 Domino [5 + 2] Cycloadditions 114
2.1.2.3.1 Cycloaddition of a Vinylic Oxirane Followed by Claisen Rearrangement 115
2.1.2.3.2 Cycloaddition of an Ynone Followed by Nazarov Cyclization 116
2.1.2.3.3 Cycloaddition of an Acetoxypyranone Followed by Conjugate Addition 116
2.1.2.3.4 Cycloaddition Cascade Involving .-Pyranone and Quinone Systems 117
2.1.3 Domino Transformations Involving an Electrocyclization Reaction 123
2.1.3.1 Metal-Mediated Cross Coupling Followed by Electrocyclization 123
2.1.3.1.1 Palladium-Mediated Cross Coupling/Electrocyclization Reactions 123
2.1.3.1.1.1 Cross Coupling/6p-Electrocyclization 123
2.1.3.1.1.2 Cross Coupling/8p-Electrocyclization 131
2.1.3.1.1.3 Cross Coupling/8p-Electrocyclization/6p-Electrocyclization 133
2.1.3.1.2 Copper-Catalyzed Tandem Reactions 139
2.1.3.1.3 Zinc-Catalyzed Tandem Reactions 139
2.1.3.1.4 Ruthenium-Catalyzed Formal [2 + 2 + 2] Cycloaddition Reactions 140
2.1.3.2 Alkyne Transformation Followed by Electrocyclization 141
2.1.3.3 Isomerization Followed by Electrocyclization 146
2.1.3.3.1 1,3-Hydrogen Shift/Electrocyclization 146
2.1.3.3.2 1,5-Hydrogen Shift/Electrocyclization 147
2.1.3.3.3 1,7-Hydrogen Shift/Electrocyclization 150
2.1.3.4 Consecutive Electrocyclization Reaction Cascades 151
2.1.3.5 Alkenation Followed by Electrocyclization 153
2.1.3.6 Electrocyclization Followed by Cycloaddition 156
2.1.3.7 Miscellaneous Reactions 157
2.1.3.7.1 Electrocyclization/Oxidation 157
2.1.3.7.2 Photochemical Elimination/Electrocyclization 158
2.1.3.7.3 Domino Retro-electrocyclization Reactions 160
2.1.3.8 Hetero-electrocyclization 160
2.1.3.8.1 Aza-electrocyclization 160
2.1.3.8.1.1 Metal-Mediated Reaction/Hetero-electrocyclization 161
2.1.3.8.1.2 Imine or Iminium Formation/Hetero-electrocyclization 169
2.1.3.8.1.3 Isomerization or Rearrangement/Hetero-electrocyclization 174
2.1.3.8.2 Oxa-electrocyclization 180
2.1.3.8.3 Thia-electrocyclization 184
2.1.4 Sigmatropic Shifts and Ene Reactions (Excluding [3,3]) 189
2.1.4.1 Practical Considerations 189
2.1.4.2 Domino Processes Initiated by Ene Reactions 190
2.1.4.3 Domino Processes Initiated by [2,3]-Sigmatropic Rearrangements 198
2.1.4.4 Domino Processes Initiated by Other Sigmatropic Rearrangements 208
2.1.4.5 Domino Processes in the Synthesis of Natural Products 213
2.1.4.6 Conclusions 221
2.1.5 Domino Transformations Initiated by or Proceeding Through [3,3]-Sigmatropic Rearrangements 225
2.1.5.1 Cope Rearrangement Followed by Enolate Functionalization 226
2.1.5.1.1 Anionic Oxy-Cope Rearrangement Followed by Intermolecular Enolate Alkylation with Alkyl Halides 226
2.1.5.1.2 Anionic Oxy-Cope Rearrangement Followed by Enolate Alkylation by Pendant Allylic Ethers 228
2.1.5.1.3 Anionic Oxy-Cope Rearrangement Followed by Enolate Acylation 229
2.1.5.2 Aza- and Oxonia-Cope-Containing Domino Sequences 231
2.1.5.2.1 Ionization-Triggered Oxonia-Cope Rearrangement Followed by Intramolecular Nucleophilic Trapping by an Enol Silyl Ether 231
2.1.5.2.2 Intermolecular 1,4-Addition-Triggered Oxonia-Cope Rearrangement Followed by Intramolecular Nucleophilic Trapping by a Nascent Enolate 233
2.1.5.2.3 Iminium-Ion-Formation-Triggered Azonia-Cope Rearrangement Followed by Intramolecular Nucleophilic Trapping by a Nascent Enamine 234
2.1.5.3 Double, Tandem Hetero-Cope Rearrangement Processes 237
2.1.5.3.1 Double, Tandem [3,3]-Sigmatropic Rearrangement of Allylic, Homoallylic Bis (trichloroacetimidates) 237
2.1.5.4 Neutral Claisen Rearrangement Followed by Further (Non-Claisen) Processes 239
2.1.5.4.1 Oxy-Cope Rearrangement/Ene Reaction Domino Sequences 239
2.1.5.4.2 Oxy-Cope Rearrangement/Ene Reaction/Claisen Rearrangement and Oxy-Cope Rearrangement/Claisen Rearrangement/Ene Reaction Domino Sequences 241
2.1.5.5 Claisen Rearrangement Followed by Another Pericyclic Process 243
2.1.5.5.1 Double, Tandem Bellus–Claisen Rearrangement Reactions 243
2.1.5.5.2 Claisen Rearrangement Followed by [2,3]-Sigmatropic Rearrangement 245
2.1.5.5.3 Claisen Rearrangement/Diels–Alder Cycloaddition Domino Sequences 247
2.1.5.5.4 Claisen Rearrangement/[1,5]-H-Shift/6p-Electrocyclization Domino Sequences 250
2.1.5.6 Claisen Rearrangement Followed by Multiple Processes 252
2.1.5.6.1 Propargyl Claisen Rearrangement Followed by Tautomerization, Acylketene Generation, 6p-Electrocyclization, and Aromatization 252
2.1.5.6.2 Propargyl Claisen Rearrangement Followed by Imine Formation, Tautomerization, and 6p-Electrocyclization 253
2.2 Intermolecular Alkylative Dearomatizations of Phenolic Derivatives in Organic Synthesis 259
2.2.1 Metal-Mediated Intermolecular Alkylative Dearomatization 262
2.2.1.1 Osmium (II)-Mediated Intermolecular Alkylative Dearomatization 262
2.2.1.2 Palladium-Catalyzed Intermolecular Alkylative Dearomatization 266
2.2.1.3 Tandem Palladium-Catalyzed Intermolecular Alkylative Dearomatization/Annulation 267
2.2.2 Non-Metal-Mediated Intermolecular Alkylative Dearomatization 270
2.2.2.1 Alkylative Dearomatizations of Phenolic Derivatives with Activated Electrophiles 270
2.2.2.2 Alkylative Dearomatizations of Phenolic Derivatives with Unactivated Electrophiles 278
2.2.3 Tandem Intermolecular Alkylative Dearomatization/Annulation 282
2.2.3.1 Tandem Alkylative Dearomatization/[4 + 2] Cycloaddition 282
2.2.3.2 Tandem Alkylative Dearomatization/Hydrogenation Followed by Lewis Acid Catalyzed Cyclization 282
2.2.3.3 Tandem Alkylative Dearomatization/Annulation To Access Type A and B Polyprenylated Acylphloroglucinol Derivatives 284
2.2.3.4 Enantioselective, Tandem Alkylative Dearomatization/Annulation 290
2.2.3.5 Tandem Alkylative Dearomatization/Radical Cyclization 293
2.2.4 Recent Methods for Alkylative Dearomatization of Phenolic Derivatives 298
2.2.4.1 Recent Applications to Intermolecular Alkylative Dearomatization of Naphthols 298
2.2.4.2 Dearomatization Reactions as Domino Transformations To Access Type A and B Polyprenylated Acylphloroglucinol Analogues 311
2.3 Additions to Alkenes and C=O and C=N Bonds 323
2.3.1 Additions to Nonactivated C=C Bonds 323
2.3.1.1 Domino Amination 324
2.3.1.1.1 Proton-Initiated Events 324
2.3.1.1.2 Transition-Metal-Initiated Events 325
2.3.1.1.3 Halogen-Initiated Events 328
2.3.1.2 Domino Etherification 335
2.3.1.2.1 Halogen-Initiated Events 336
2.3.1.3 Domino Carbonylation 347
2.3.1.3.1 Transition-Metal-Initiated Events 347
2.3.1.3.2 Halogen-Initiated Events 350
2.3.1.4 Domino Polyene Cyclization 352
2.3.1.4.1 Transition-Metal-Initiated Events 353
2.3.1.4.2 Halogen-Initiated Events 355
2.3.1.4.3 Chalcogen-Initiated Events 359
2.3.2 Organocatalyzed Addition to Activated C=C Bonds 367
2.3.2.1 Organocatalyzed Domino Reactions with Activated Alkenes: The First Examples 367
2.3.2.1.1 Prolinol Trimethylsilyl Ethers as Privileged Catalysts for Enamine and Iminium Ion Activation 374
2.3.2.1.2 Increasing Complexity in Organocatalyzed Domino Reactions 377
2.3.2.2 Domino Organocatalyzed Reactions of Oxindole Derivatives 379
2.3.2.2.1 From Enders' Domino Reactions to Melchiorre's Methylene Oxindole 380
2.3.2.2.2 Michael Addition to Oxindoles 387
2.3.2.3 Synthesis of Tamiflu: The Hayashi Approach 395
2.3.2.4 One-Pot Synthesis of ABT-341, a DPP4-Selective Inhibitor 402
2.3.2.5 Large-Scale Industrial Application of Organocatalytic Domino Reactions: A Case Study 406
2.3.2.5.1 Transferring Organocatalytic Reactions from Academia to Industry: Not Straightforward 406
2.3.2.5.2 The Reaction Developed in the Academic Environment 407
2.3.2.5.3 The Reaction Developed in the Industrial Environment 409
2.3.3 Addition to Monofunctional C=O Bonds 417
2.3.3.1 Transition-Metal-Catalyzed Domino Addition to C=O Bonds 417
2.3.3.1.1 Domino Reactions Involving Carbonyl Ylides 417
2.3.3.1.2 Reductive Aldol Reactions 419
2.3.3.1.3 Michael/Aldol Reactions 423
2.3.3.1.4 Other Domino Addition Reactions 424
2.3.3.2 Organocatalytic Domino Addition to C=O Bonds 425
2.3.3.2.1 Amine-Catalyzed Domino Addition to C=O Bonds 425
2.3.3.2.1.1 Enamine-Catalyzed Aldol/Aldol Reactions 425
2.3.3.2.1.2 Enamine-Catalyzed Aldol/Michael Reactions 426
2.3.3.2.1.3 Enamine-Catalyzed Diels–Alder Reactions 427
2.3.3.2.1.4 Enamine-Catalyzed Michael/Henry Reactions 429
2.3.3.2.1.5 Enamine-Catalyzed Michael/Aldol Reactions 430
2.3.3.2.1.6 Enamine-Catalyzed Michael/Hemiacetalization Reactions 430
2.3.3.2.1.7 Iminium-Catalyzed Michael/Aldol Reactions 432
2.3.3.2.1.8 Iminium-Catalyzed Michael/Henry Reactions 434
2.3.3.2.1.9 Iminium-Catalyzed Michael/Morita–Baylis–Hillman Reactions 434
2.3.3.2.1.10 Iminium-Catalyzed Michael/Hemiacetalization Reactions 435
2.3.3.2.2 Thiourea-Catalyzed Domino Addition to C=O Bonds 435
2.3.3.2.2.1 Aldol/Cyclization Reactions 435
2.3.3.2.2.2 Michael/Aldol Reactions 436
2.3.3.2.2.3 Michael/Henry Reactions 437
2.3.3.2.2.4 Michael/Hemiacetalization Reactions 438
2.3.3.2.3 Phosphoric Acid Catalyzed Domino Addition to C=O Bonds 440
2.3.3.3 Lewis Acid Catalyzed Domino Addition to C=O Bonds 441
2.3.3.4 Conclusions 444
2.3.4 Additions to C=N Bonds and Nitriles 449
2.3.4.1 Addition to C=N Bonds and the Pictet–Spengler Strategy 452
2.3.4.2 Ugi Five-Center Four-Component Reaction Followed by Postcondensations 458
2.3.4.3 Addition to Nitriles 469
Keyword Index 479
Author Index 511
Abbreviations 527
Abstracts
2.1.1 The Diels–Alder Cycloaddition Reaction in the Context of Domino Processes
J. G. West and E. J. Sorensen
The Diels–Alder cycloaddition has been a key component in innumerable, creative domino transformations in organic synthesis. This chapter provides examples of how this [4 + 2] cycloaddition has been incorporated into the said cascades, with particular attention to its interplay with the other reactions in the sequence. We hope that this review will assist the interested reader to approach the design of novel cascades involving the Diels–Alder reaction.
Keywords: Diels–Alder • cascade • domino reactions • pericyclic • [4 + 2] cycloaddition
2.1.2 Domino Reactions Including [2 + 2], [3 + 2], or [5 + 2] Cycloadditions
I. Coldham and N. S. Sheikh
This chapter covers examples of domino reactions that include a [2 + 2]-, [3 + 2]-, or [5 + 2]-cycloaddition reaction. The focus is on concerted reactions that occur in a tandem sequence in one pot, rather than overall “formal cycloadditions” or multicomponent couplings. The cycloaddition step typically involves an alkene or alkyne as one of the components in the ring-forming reaction. In addition to the key cycloaddition step, another bond-forming reaction will be involved that can precede or follow the cycloaddition. This other reaction is often an alkylation that generates the substrate for the cycloaddition, or is a ring-opening or rearrangement reaction that occurs after the cycloaddition. As the chemistry involves sequential reactions including at least one ring-forming reaction, unusual molecular structures or compounds that can be difficult to prepare by other means can be obtained. As a result, this strategy has been used for the regio- and stereoselective preparation of a vast array of polycyclic, complex compounds of interest to diverse scientific communities.
Keywords: alkylation • [2 + 2] cycloaddition • [3 + 2] cycloaddition • [5 + 2] cycloaddition • dipolar cycloaddition • domino reactions • Nazarov cyclization • ring formation • [3,3]-sigmatropic rearrangement • tandem reactions
2.1.3 Domino Transformations Involving an Electrocyclization Reaction
J. Suffert, M. Gulea, G. Blond, and M. Donnard
Electrocyclization processes represent a powerful and efficient way to produce carbo- or heterocycles stereoselectively. Moreover, when electrocyclizations are involved in domino processes, the overall transformation becomes highly atom and step economic, enabling access to structurally complex molecules. This chapter is devoted to significant contributions published in the last 15 years, focusing on synthetic methodologies using electrocyclization as a key step in a domino process.
Keywords: electrocyclization • hetero-electrocyclization • domino reactions • cascade reactions
2.1.4 Sigmatropic Shifts and Ene Reactions (Excluding [3,3])
A. V. Novikov and A. Zakarian
This chapter features a review and discussion of the domino transformations initiated by ene reactions and sigmatropic rearrangements, particularly focusing on [2,3]-sigmatropic shifts, such as Mislow–Evans and Wittig rearrangements, and [1,n] hydrogen shifts. A variety of examples of these domino processes are reviewed, featuring such follow-up processes to the initial reaction as additional ene reactions or sigmatropic shifts, Diels–Alder cycloaddition, [3 + 2] cycloaddition, electrocyclization, condensation, and radical cyclization. General practical considerations and specific features in the examples of the reported cascade transformation are highlighted. To complete the discussion, uses of these cascade processes in the synthesis of natural products are discussed, demonstrating the rapid assembly of structural complexity that is characteristic of domino processes. Overall, the domino transformations initiated by ene reactions and sigmatropic shifts represent an important subset of domino processes, the study of which is highly valuable for understanding key aspects of chemical reactivity and development of efficient synthetic methods.
Keywords: ene reaction • sigmatropic shift • domino reactions • cascade reactions • hydrogen shift • [1,3]-shift • [1,5]-shift • [1,7]-shift • [2,3]-shift • [3,3]-shift • Mislow–Evans rearrangement • Wittig rearrangement • Diels–Alder cycloaddition • Claisen rearrangement • oxy-Cope rearrangement • electrocyclization • chloropupukeanolide D • isocedrene • steroids • mesembrine • joubertinamine • pinnatoxins • sterpurene • arteannuin M • pseudomonic acid A
2.1.5 Domino Transformations Initiated by or Proceeding Through [3,3]-Sigmatropic Rearrangements
C. A. Guerrero
This chapter concerns itself with domino transformations (i.e., cascade sequences and/or tandem reactions) that are either initiated by or proceed through at least one [3,3]-sigmatropic rearrangement. Excluded from this discussion are domino transformations that end with sigmatropy. The reactions included contain diverse forms of [3,3]-sigmatropic rearrangements and are followed by both polar chemistry or further concerted rearrangement.
Keywords: rearrangement • sigmatropic • Bellus–Claisen • Cope • Overman • concerted • stereoselective • stereospecific • ene • trichloroacetimidate • Diels–Alder
2.2 Intermolecular Alkylative Dearomatizations of Phenolic Derivatives in Organic Synthesis
J. A. Porco, Jr., and J. Boyce
Intermolecular alkylative dearomatization products have shown promise as synthetic intermediates with diverse capabilities. This chapter describes the available methods for constructing these dearomatized molecules and demonstrates their value as synthetic intermediates for efficient total syntheses.
Keywords: alkylative dearomatization • dearomative alkylation • dearomative substitution • domino transformations • domino sequences • dearomative domino transformations • cationic cyclization • radical cyclization • alkylative dearomatization/annulation
2.3.1 Additions to Nonactivated C=C Bonds
Z. W. Yu and Y.-Y. Yeung
Electrophilic additions to nonactivated C=C bonds are one of the well-known classical reactions utilized by synthetic chemists as a starting point to construct useful complex organic molecules. This chapter covers a collection of electrophile-initiated domino transformations involving alkenes as the first reaction, followed by reaction with suitable nucleophiles in the succession and termination reactions under identical conditions. The discussion focuses on recent advances in catalysis, strategically designed alkenes, and new electrophilic reagents employed to improve reactivity and control of stereochemistry in the sequence of bond-forming steps.
Keywords: nonactivated alkenes • addition • domino reactions • amination • etherification • carbonylation • polyenes • protons • halogens • transition metals • chalcogens
2.3.2 Organocatalyzed Addition to Activated C=C Bonds
P. Renzi, M. Moliterno, R. Salvio, and M. Bella
In this chapter, several examples of organocatalyzed additions to C=C bonds carried out through a domino approach are reviewed, from the early examples to recent applications of these strategies in industry.
Keywords: organocatalysis • domino reactions • iminium ions • enamines • Michael/aldol reactions • nucleophilic/electrophilic addition • α,β-unsaturated carbonyl compounds • spirocyclic oxindoles • cinchona alkaloid derivatives • chiral secondary amines • Knoevenagel condensation • methyleneindolinones
2.3.3 Addition to Monofunctional C=O Bonds
A. Song and W. Wang
Catalytic asymmetric domino addition to monofunctional C=O bonds is a powerful group of methods for the rapid construction of valuable chiral building blocks from readily available substances. Impressive progress has been made on transition-metal-catalyzed and organocatalytic systems that promote such addition processes through reductive aldol, Michael/aldol, or Michael/Henry sequences. In addition, Lewis acid catalysis has also been developed in this area for the synthesis of optically active chiral molecules. This chapter covers the most impressive examples of these recent developments in domino chemistry.
Keywords: aldol reactions • carbonyl ylides • chiral amine catalysis • domino reactions • epoxy alcohols • Lewis acid catalysis • Michael addition • organocatalysis • phosphoric acid catalysis • thiourea catalysis
2.3.4 Additions to C=N Bonds and Nitriles
E. Kroon, T. Zarganes Tzitzikas, C. G. Neochoritis, and A. Dçmling
This chapter describes additions to imines and nitriles and their post-modifications within the context of domino reactions and multicomponent reaction chemistry.
Keywords: multicomponent...
| Erscheint lt. Verlag | 11.5.2016 |
|---|---|
| Co-Autor | Marco Bella, Alexander Dömling, Jon Boyce, Gaelle Blond, Iain Coldham |
| Verlagsort | Stuttgart |
| Sprache | englisch |
| Themenwelt | Naturwissenschaften ► Chemie ► Organische Chemie |
| Technik | |
| Schlagworte | Dearomatization • domino transformation • Metal-Mediated Transformation • Metathesis • Natural Products • Organic Chemistry • organic synthesis • organic transformation • Organische Synthese • Pericyclic reaction • Radical chemistry • reference work • Synthetic Methods |
| ISBN-10 | 3-13-221171-0 / 3132211710 |
| ISBN-13 | 978-3-13-221171-1 / 9783132211711 |
| Haben Sie eine Frage zum Produkt? |
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