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Asymmetric Synthesis V3

1st Edition - April 1, 1984

Editor: James Morrison

eBook ISBN:

9 7 8 - 0 - 3 2 3 - 1 4 5 0 0 - 8

Asymmetric Synthesis, Volume 3: Stereodifferentiating Addition Reactions, Part B presents intensive investigations in leading academic and industrial laboratories on… Read more

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Asymmetric Synthesis, Volume 3: Stereodifferentiating Addition Reactions, Part B presents intensive investigations in leading academic and industrial laboratories on stereodifferentiating addition reactions. This book is divided into eight chapters and begins with a comprehensive review of the formation of chiral metal enolates and their stereoselective alkylation reactions. These topics are followed by discussions on chiral Aldol addition reactions and the many variations of asymmetric synthesis that may be carried out using chiral oxazolines. A chapter describes the alkylation of chiral hydrazones, a process that yields chiral-substituted aldehydes and ketones. Other chapters explore a variety of cyclization processes that form carbon-carbon and carbon-heteroatom bonds. The last chapters deal with the asymmetric cycloadditions and sigma-tropic rearrangements. Synthetic chemists and researchers will find this book invaluable.

Contributors

Preface

1. Stereoselective Alkylation Reactions of Chiral Metal Enolates

I. Prologue

II. Selective Enolate Formation

III. Enolate Structure

IV. Transition-State Control Elements

V. Intraannular Chirality Transfer

VI. Chelate-Enforced Intraannular Chirality Transfer

VII. Extraannular Chirality Transfer

VIII. Conclusions

References

2. The Aldol Addition Reaction

I. Simple Diastereoselection

II. Diastereofacial Selectivity

References

3. Asymmetric Synthesis via Chiral Oxazolines

I. Introduction

II. (R)- and (S)-Dialkylacetic Acids

III. (R)- or (S)-2-Substituted Butyrolactones and Valcrolactones

IV. Optically Active ß-Hydroxy and ß-Methoxy Acids

V. ß-Hydroxy Esters via Aldol Condensation

VI. Optically Active 2-Methoxyalkanoic and 2-Chloroalkanoic Acids

VII. Thiiranes

VIII. Asymmetric Reductions

IX. Chiral Grignard Reagents

X. Kinetic Resolution of Racemic Alkyl Halides

XI. Optically Active 2-Hydroxycarboxylic Acids

XII. Chiral Phthalides

XIII. (R)- and (S)-ß,ß-Dialkylpropionic Acids

XIV. (R)- and (S)-ß-Substituted Valerolactones

XV. α,ß,ß-Trisubstituted Propionic Acids

XVI. (S)-4-Substituted 1,4-Dihydropyridines

XVII. Chiral Binaphthyls

References

4. Alkylation of Chiral Hydrazones

I. Introduction

II. The SAMP-/RAMP-Hydrazone Method

III. Asymmetric Carbon-Carbon Bond Formations α to the Carbonyl Group via SAMP-/RAMP- Hydrazones

IV. Mechanistic Studies

V. Applications of the SAMP-/RAMP-Hydrazone Method to Asymmetric Syntheses of Natural Products

VI. Conclusion and Outlook

References

5. Olefin Cyclization Processes That Form Carbon-Carbon Bonds

I. Introduction

II. Ring Fusion: Relationship between Chiral Centers A and B

III. Orientation of Adjacent Rings: Relationship between Chiral Centers A and C

IV. Effect of a Substituent on Ring 1 on the Chirality of Cyclization: Influence of Chiral Center D

V. Effect of a Substituent on Ring 2 on the Chirality of Cyclization: Influence of Chiral Center E

VI. Stereochemistry of Termination: Relationship between Chiral Center F and the Others

VII. Chiral Auxiliaries

VIII. Mechanistic Conclusions: Are the Cyclizations Concerted or Stepwise?

References

6. Olefin Cyclization Processes That Form Carbon-Heteroatom Bonds

I. Introduction

II. Formation of Oxygen Heterocycles

III. Formation of Nitrogen Heterocycles

IV. Formation of Sulfur Heterocycles

References

7. Asymmetric Cycloaddition Reactions

I. Introduction

II. Intermolecular Diels-Alder Reactions

III. Intramolecular Diels-Alder Processes

IV. [2 + 2] Cycloadditions

V. [3 + 2] Cycloadditions

References

8. Chirality Transfer via Sigmatropic Rearrangements

I. Introduction

II. 3,3-Sigmatropic Rearrangements

III. 2,3-Sigmatropic Rearrangements

IV. Summary

References

Index