Heterocycles as Chiral Auxiliaries in Asymmetric Synthesis

Preface
Contents
Carbohydrates as Stereodifferentiating Auxiliaries
1 Introduction
2 Cycloaddition Reactions
2.1 [4 + 2] Cycloaddition Reactions: Diels-Alder Reactions and 1,3-Diploar Cycloadditions Reactions
2.1.1 Carbohydrate-Linked Dienophiles
2.1.2 Carbohydrate-Linked Dienes and 1,3-Dipoles
2.1.3 Carbohydrate-Derived 1,3-Dipoles
2.2 [2 + 2] Cycloaddition Reactions
2.3 [2 + 1] Cycloaddition Reactions
3 Reactions of Glycosylamines: Mannich-Type Reactions
3.1 Strecker and Ugi Reactions for the Synthesis of Amino Acids
3.2 Aminophosphonic Acid Derivatives
3.3 Mannich Reaction with Silylketene Acetals or Bis-Silylketene Acetals; β-Amino Acids
3.4 Homoallylamines
3.5 Mannich-Type Reaction of Aromatic Compounds and Electron-Rich Alkenes
3.6 Reactions with Silyl Dienol Ethers: Domino Mannich-Michael Cascades
3.7 Stereocontrolled Transformations of N-Glycosyl Dehydropiperidinones
3.7.1 Synthesis of 2,6-Substituted Piperidines
3.7.2 Stereoselective Synthesis of 3-, 4- and 5-Substituted Piperidine Derivatives
3.8 Stereoselective Total Syntheses of Alkaloids Using Glycosylamines as the Auxiliaries
3.8.1 Alkaloids with cis- or trans-Annelated Decahydroquinoline Structure
3.8.2 Diastereotopic Protonation and Deprotonation Directed by the Carbohydrate Auxiliary: Total Synthesis of Indolizidines fr...
3.8.3 Total Synthesis of Tetraponerines T8 and T7: The Matched/Mismatched Cases
3.9 Are 2,6-trans-Disubstituted Piperidines Stereoselectively Accessible via Glycosylamines?
4 N-Glycosylation in Order to Induce Reactivity and Stereodifferentiation
4.1 Glycosylation for Stereodifferentiation of Enantiotopic Sides of Aromatic N-Heterocycles
4.2 Glycosylation-Induced Stereoselective Reactions of Achiral Imines
4.3 Properties of the O-Pivaloyl Group in Carbohydrate Auxiliaries
5 Carbohydrate Auxiliaries in Conjugate Addition Reactions
5.1 Carbohydrate Auxiliaries in Diastereoselective Michael Addition of Ester Enolates
5.2 Bicyclic Carbohydrate Oxazolidinones as the Auxiliaries in Conjugate Addition Reactions of Organoaluminum Compounds
6 Conclusion and Outlook
References
Boron-Containing Chiral Auxiliaries
1 Introduction
2 Overview
3 Diastereoselective Synthesis
3.1 Cycloadditions
3.1.1 Epoxidation, Cyclopropanation
3.1.2 [4 + 2]-Cycloadditions
3.1.3 1,3-Dipolar Cycloadditions
3.2 Matteson Homologations
3.3 SN2´ Reactions
3.4 Carbonyl Allylation
3.5 [3,3]-Sigmatropic Rearrangement
3.6 Remote-Controlled Reactions
4 Applications in Asymmetric Synthesis
References
Oxazolidinones and Related Heterocycles as Chiral Auxiliaries/Evans and Post-Evans Auxiliaries
1 Introduction
2 Synthesis of Optically Active Oxazolidinones
3 Optically Active Oxazolidinones as Chiral Auxiliaries
3.1 Diastereoselective α-Functionalization of Optically Active Oxazolidinones
3.2 Diastereoselective Aldol Reactions and Related Transformations
3.3 Diastereoselective Transformations of α,β-Unsaturated Acyl-oxazolidinones
3.4 Diastereoselective Reactions of Vinyl-, Alkynyl-, or Allenenyl-oxazolidinones
3.5 Diastereoselective C(1)-Transformations of Oxazolidinone Derivatives
References
Pyrrolidines as Chiral Auxiliaries
1 Introduction
2 Pyrrolidine Auxiliaries in α-Alkylation Reactions
3 Pyrrolidine Auxiliaries in Aldol Reactions
4 Pyrrolidine Auxiliaries in Michael Reactions
5 Pyrrolidine Auxiliaries in Rearrangements
6 Pyrrolidine Auxiliaries in Nucleophilic Additions to C=N Bonds
7 Pyrrolidine Auxiliaries in Cycloadditions
8 Pyrrolidine Auxiliaries in Birch Reductions
9 Pyrrolidine Auxiliaries in Organometallic Chemistry
10 CrossLinkingellaneous Applications of Pyrrolidine Auxiliaries
References
Synthesis and Utility of Hetero- and Non-heterocyclic Chiral Auxiliaries Derived from Terpenes: Camphor and Pinene
1 Introduction
2 Camphor Auxiliaries
2.1 Camphor Imine
2.2 Camphor Methyl Ketone Enolate Derivatives
2.3 Camphor Homoallylic Alcohol
2.4 Camphor α-Hydroxy Enone 14
3 Functionalized Camphor Auxiliaries
3.1 A Camphor-Derived δ-Lactol Auxiliary
3.2 Hydroxyisoborneol Auxiliaries
3.3 Camphor-Derived Auxiliary Cis-3-[N-(Aryl)Benzenesulfonamido]Borneol 34
3.3.1 Aldol Reactions Using Borneol Auxiliaries 34
3.4 Camphor Oxazolidinones as Chiral Auxiliaries
4 Camphor-Based Oxazolidinone O-60 and Oxazolidinethione S-60 Chiral Auxiliaries
5 Sultam- and Sulfonamide-Derived Camphor Auxiliaries
6 The Aza Camphor Class of Auxiliaries
6.1 Introduction
6.2 2- and 3-Aza Camphor Lactams and Related Derivatives
6.2.1 Preparation of 2-Aza Camphor Lactam (91) and 3-Aza Camphor Lactam (94)
6.2.2 8-Phenyl-3-Aza and 10-Phenyl-3-Aza Camphor Lactams 97 and 103
6.2.3 Unsaturated or Rearranged Camphor Lactams 105 and 108
6.3 Applications of 2-Aza Camphor Lactam (91)
6.3.1 Attachment of Reactive Subunits
6.3.2 Applications to Diels-Alder Reactions
6.3.3 Aldol Reactions
6.3.4 Alkylation Reactions
6.3.5 Acylation Reactions
6.3.6 Sequential Homologation-Alkylation
6.3.7 Oxidative Acetal Formation
6.3.8 Preparation and Reactions of Chiral Ynamides Derived from 91
6.3.9 [2,3]-Meisenheimer Rearrangements
6.4 Applications of 1,7,7-Trimethyl-3-Azabicyclo[2.2.1]-Heptan-2-one (94)
6.4.1 Attachment of Reactive Subunits
6.4.2 Applications of 94 to Diels-Alder Reactions
6.4.3 Applications of 94 to Aldol Reactions
6.4.4 Applications of 94 to Alkylation Reactions
6.4.5 Applications of 94 to Enolate C-Acylation Reactions
6.4.6 Olefination of Aldehydes
6.4.7 Application to Diastereoselective Anchimerically Assisted Substitution
6.4.8 Oxidative Acetal Formation
6.4.9 Preparation and Reactions of Chiral Ynamides Derived from 94
6.5 Applications of (105)
6.5.1 Attachment of Reactive Subunits
6.5.2 Diels-Alder Reactions of Dienophiles Derived from 105
6.5.3 Aldol Reactions of Acylated Derivatives of 105
6.6 Applications of 6,6-Dimethyl-3-Aza Camphor Lactam (108)
6.6.1 Acylation of Lactam 108
6.6.2 Application of Acylated Derivatives of 108 to the Diels-Alder Reaction
6.6.3 Application of Acylated Derivatives of 108 to Aldol Reactions
6.6.4 Acylation of Lactam ent-108 with the Bestmann Ylide
6.7 Applications of 8-Phenyl-3-Azabicyclo[2.2.1]Heptan-3-One (97)
6.7.1 Attachment of Reactive Subunits
6.7.2 Application of Imide Derivatives of 97 to Diels-Alder Reactions
6.8 Auxiliary Removal and Recovery
7 Auxiliaries Derived from Pinene
7.1 A Chiral Auxiliary Derived from α-Pinene (2)
7.2 Chiral Alcohol Auxiliaries Derived from β-Pinene (3)
7.3 Pinene-Derived Lactam Auxiliaries
7.3.1 Preparation of Pinene-Derived Lactam 244
7.3.2 Diels-Alder Reactions of Imide Dienophiles Derived from 244
7.3.3 Diels-Alder Reactions of Dienophiles 247 and 248 Derived from Pinene
8 Concluding Remarks
References
Heterocyclic Chiral Auxiliaries in Total Synthesis of Natural Products
1 Introduction
2 Oxazolidinone-Based Chiral Auxiliaries
2.1 (+)-Brefeldin A
2.2 Baulamycin A
2.3 Calcaripeptides A-C
2.4 Glucolipsin A
2.5 Apoptolidinone
2.6 Bleomycin A
2.7 Brasilinolide A
2.8 FD-891
2.9 (-)-FR182877
3 Pyrrolidine-Based Chiral Auxiliaries
3.1 (+)-Streptenol A
3.2 (-)-α-Elemene
3.3 (-)-Neonepetalactone, Dehydroiridodial, and Dehydroiridodiol
3.4 (+)-Sordidin
3.5 (-)-Callystatin A
4 Sulfur-Based Chiral Auxiliaries
4.1 (-)-Manzacidin B
4.2 (+)-Bakuchiol
5 Phosphorous-Based Chiral Auxiliaries
5.1 Methyl Jasmonate
5.2 (-)-Anthoplalone
5.3 (-)-Berkelic Acid
5.4 (+)-Ambruticin S
5.5 Estrone
5.6 Nudiflosides A and D
6 Imidazolidinone-Based Chiral Auxiliaries
6.1 (-)-Lavandulol
7 Pyrimidinone-Based Chiral Auxiliaries
7.1 Oxyneolignan
8 Oxazolinyl Ketone as Chiral Auxiliaries
8.1 (-)-Rhazinilam
References
Correction to: Carbohydrates as Stereodifferentiating Auxiliaries
Correction to: Chapter ``Carbohydrates as Stereodifferentiating Auxiliaries´´ in: Horst Kunz and Alexander Stoye, Top Heterocy...
Correction to: Oxazolidinones and Related Heterocycles as Chiral Auxiliaries/Evans and Post-Evans Auxiliaries
Correction to: Chapter ``Oxazolidinones and Related Heterocycles as Chiral Auxiliaries/Evans and Post-Evans Auxiliaries´´ in: ...
Correction to: Pyrrolidines as Chiral Auxiliaries
Correction to: Chapter ``Pyrrolidines as Chiral Auxiliaries´´ in: Wolfgang Maison, Top Heterocycl Chem, DOI: 10.1007/7081_2019...
Index