The Isoquinoline Alkaloids Chemistry and Pharmacology

The Isoquinoline Alkaloids: Chemistry and Pharmacology presents an overview of the chemistry, biogenesis, spectroscopy, and pharmacology of the isoquinoline alkaloids. This book examines the significant and interesting aspects of alkaloids. Organized into 32 chapters, this book starts with a discussion of the biogenesis of the isoquinolines and the various pharmacological effects of simple tetrahydroisoquinolines that have stimulant and convulsive properties. This text then explores the infrared absorptions, with emphasis on wavelength and frequency. Other chapters include topics on synthesis, degradation, reactions, absolute configuration, as well as on ultraviolet and nuclear magnetic resonance spectroscopy. This book further explores the various methods available for the preparation of simple tetrahydroisoquinolines, including the Bischler–Napieralski, Pictet–Spengler, and phenolic cyclization, as well as the Friedel–Crafts acylation. The last chapter deals with ancistrocladine, which is the first isoquinoline alkaloid found to possess a methyl group. Biochemists and biophysicists will find this book useful.

Preface

Chapter 1. The Simple Tetrahydroisoquinolines

I. Introduction

II. Degradations

III. Some Nonbasic Isoquinolines: Peyoglutam, Mescalotam, and Related Alkaloids

IV. Methods of Synthesis

V. The Gigantine Problem

VI. Some Reactions of Tetrahydroisoquinolines and Their Derivatives

VII. Absolute Configuration

VIII. Biosynthesis

IX. Pharmacology

X. The Possible Role of Tetrahydroisoquinoline Alkaloids in Alcoholism

XI. Mass Spectroscopy

XII. NMR Spectroscopy

XIII. UV Spectroscopy

References

Chapter 2. The Benzylisoquinolines

I. Introduction

II. Degradation of Laudanosine, A Tetrahydro Benzylisoquinoline Alkaloid

III. Structural Elucidation of Takatonine, A Quaternary Benzylisoquinoline Alkaloid

IV. Petaline, A Tetrahydro Benzylisoquinoline of Unusual Substitution Pattern

V. Two Glycosidic Tetrahydrobenzylisoquinoline Alkaloids: Latericine and Veronamine

VI. Methods of Synthesis

VII. Some Reactions of Benzylisoquinolines

VIII. Absolute Configuration

IX. Biosynthesis

X. Pharmacology

XI. A Possible Biochemical Basis for Alcohol Addiction: A Hypothesis and Its Critique

XII. Mass Spectroscopy

XIII. NMR Spectroscopy

XIV. X-Ray Analysis

XV. UV Spectroscopy

References

Chapter 3. The Isoquinolones

I. Introduction

II. Structural Elucidation and Synthesis

III. An Alternate Synthesis of 3,4-Dihydroisoquinolones

IV. Pharmacology

References

Chapter 4. The Pavines and Isopavines

I. Structural Elucidation and Synthesis

II. Absolute Configuration

III. Biosynthesis

IV. Mass Spectroscopy

V. NMR Spectroscopy

VI. UV Spectroscopy

VII. The Differentiation between Pavine and Isopavine Bases

References

Chapter 5. The Bisbenzylisoquinolines

I. Introduction

II. A Classical Degradation of a Bisbenzylisoquinoline Alkaloid: The Structure of Berbamine

III. Some Comments on the Sodium in Liquid Ammonia Cleavage of Bisbenzylisoquinolines

IV. The Structures of Tubocurarine, Chondocurarine, and Chondocurine

V. Repanduline: A Ketonic Bisbenzylisoquinoline Alkaloid

VI. Syntheses of Bisbenzylisoquinolines

VII. Conversion of Oxyacanthine-type Alkaloids to the Trilobine Series

VIII. Some Reagents for Interrelating Benzylisoquinolines, Bisbenzylisoquinolines, and Other Isoquinolines

IX. Biogenesis and Phenolic Oxidative Coupling

X. Pharmacology

XI. Absolute Configuration

XII. The Isomerization of (-f-)-Oxyacanthine to (—)-Repandine

XIII. Mass Spectroscopy

XIV. NMR Spectroscopy

XV. UV Spectroscopy

References

Chapter 6. The Cularines

I. Introduction

II. Cularine: Structural Determination

III. Syntheses of Cularine and Its Analogs

IV. Absolute Configuration

V. NMR Spectroscopy and Conformation

VI. Mass Spectroscopy

VII. UV Spectroscopy

References

Chapter 7. The Cularine-Morphine Dimers

I. Structural Elucidation

II. Dehydrocancentrine A and Dehydrocancentrine Β

III. UV Spectroscopy

References

Chapter 8. The Dibenzopyrrocolines

I. Structural Elucidation

II. Syntheses of Dibenzopyrrocolines

III. Mass Spectroscopy

IV. NMR Spectroscopy

References

Chapter 9. The Proaporphines

I. Introduction

II. Structural Elucidation

III. Nonbiogenetic Syntheses

IV. Biogenetic Studies Using Phenolic Oxidative Coupling

V. Biogenetic Studies with Labeled Compounds

VI. Absolute Configuration and Circular Dichroism

VII. Pharmacology

VIII. Mass Spectroscopy

IX. NMR Spectroscopy

X. UV and IR Spectroscopy

References

Chapter 10. The Aporphines

I. Introduction

II. A Classical Degradation of an Aporphine

III. Apomorphine

IV. Nonbiogenetic Syntheses of Aporphines

V. Some Reactions of Aporphines

VI. Stereochemistry and Absolute Configuration

VII. X-Ray Crystallography

VIII. Biosynthesis and Biogenetic Syntheses

IX. The Relationship between the Ring D Substituents and the Absolute Configuration

X. Pharmacology

XI. Mass Spectroscopy

XII. NMR Spectroscopy

XIII. UV Spectroscopy

XIV. Ushinsunine: A C-7 Hydroxylated Aporphine

XV. Steporphine: A C-4 Hydroxylated Aporphine

XVI. The Dehydroaporphines

References

Chapter 11. Pakistanamine: A Proaporphine-Benzylisoquinoline Dimer

I. Structural Elucidation and Chemical Conversions

II. Mass Spectroscopy

III. NMR Spectroscopy

IV. UV and IR Spectroscopy

Reference

Chapter 12. The Aporphine-Benzylisoquinoline Dimers

I. Introduction

II. Structural Elucidation and Synthesis

III. Biosynthesis

IV. Pharmacology

V. Circular Dichroism

VI. NMR Spectroscopy

VII. UV Spectroscopy

VIII. (H-)-Hernandaline, An Elaborated Aporphine Alkaloid 239

IX. The Kupchan-Liepa Total Synthesis of (+)-Thalicarpine via Synthetic (+)-Hernandaline

X. Pakistanine, A Novel Type Aporphine-Benzylisoquinoline Dimer

References

Chapter 13. The Oxoaporphines

I. Introduction

II. Liriodenine: Structural Elucidation and Synthesis

III. The Oxidation of Aporphines and the Reduction of Oxoaporphines

IV. An Unusual Demethoxylation Reaction

V. Pharmacology

VI. NMR Spectroscopy

VII. UV Spectroscopy

VIII. Corunnine and Pontevedrine, Two New Oxoaporphines

References

Chapter 14. The Phenanthrene Alkaloids

I. Structural Elucidation and Synthesis

II. Pharmacology

III. Mass Spectroscopy

IV. NMR Spectroscopy

V. UV Spectroscopy

References

Chapter 15. Taspine

I. Structural Elucidation

II. Biogenesis and Conversion of Magnoflorine into Taspine

III. NMR and UV Spectroscopy

References

Chapter 16. The Protoberberines and Retroprotoberberines

I. Introduction

II. Chemical Degradation

III. Syntheses of Protoberberines

IV. Reactions of Protoberberines

V. Stereochemistry

VI. Berberastine and Thalidastine: Two Quaternary Protoberberines Hydroxylated at C-5

VII. Mecambridine and Alkaloid PO-5, Orientalidine and Alkaloid PO-4: Four Retroprotoberberine Alkaloids

VIII. Color Changes of Phenolic Quaternary Protoberberines

IX. Biosynthesis

X. Pharmacology

XI. Mass Spectroscopy

XII. NMR Spectroscopy

XIII. UV Spectroscopy

References

Chapter 17. The Benzophenanthridines

I. Introduction

II. The Chemistry and Stereochemistry of Chelidonine

III. The Chemistry of Sanguinarine and Chelerythrine

IV. The Structures of Corynoline and Corynoloxine: Two Unusual Benzophenanthridine Alkaloids

V. Syntheses of Benzophenanthridines

VI. Mass Spectroscopy

VII. NMR Spectroscopy

VIII. The C-6-Methoxylated Aromatic Benzophenanthridines

IX. Bocconine

X. Bocconoline and Corynolamine

XI. The Characterization of a Dimeric Benzophenanthridine Alkaloid

XII. Biosynthesis

XIII. Pharmacology

XIV. UV Spectroscopy

References

Chapter 18. The Protopines

I. Introduction

II. Structural Elucidation of Cryptopine and Protopine

III. Formation of Protoberberines from Protopines

IV. The Chemistry of Anhydrocryptopine and the Conversion of Protopine to Sanguinarine

V. The Conversion of Tetrahydroprotoberberines into Protopine Bases

VI. Mass Spectroscopy

VII. 13-Oxomuramine, A Protopine Base Oxygenated at C-13

VIII. Fumaridine and Fumaramine, Two New Protopine Alkaloids?

IX. Biosynthesis

X. Pharmacology

XI. NMR Spectroscopy

XII. X-Ray Analysis

XIII. UV Spectra

References

Chapter 19. The Phthalic Isoquinolines

I. Introduction

II. Structural Elucidation

III. Absolute Configuration and ORD Studies

IV. Syntheses of Phthalide Isoquinolines

V. Some Reactions of Narcotine and Hydrastine

VI. Biosynthesis

VII. Pharmacology

VIII. Mass Spectroscopy

IX. NMR Spectroscopy

X. UV Spectroscopy

References

Chapter 20. The Spiro Benzylisoquinolines

I. Introduction and Nomenclature

II. Structural Elucidation

III. Syntheses of Spiro Benzylisoquinolines

IV. The Protoberberine->Spiro Benzylisoquinoline->Dibenzo Cyclopent[b]- azepine Rearrangement

V. Mass Spectroscopy

VI. UV Spectroscopy

References

Chapter 21. The Rhoeadines and Papaver Rubines

I. Introduction

II. Reactions of Rhoeadine and Derivatives

III. An Alternate Degradative Scheme

IV. Isomerization of the Rhoeadines and Relative Stereochemistry: NMR Spectroscopy

V. (+)-lsorhoeagenine α-D-Glucoside

VI. Conversion of Rhoeadine to the Protoberberine Alkaloidal Salt Coptisine

VII. Acid-Catalyzed Rearrangement of the Papaverrubines

VIII. Some Early Preparations of Benzazepine Systems

IX. The Conversion of a Spiro Benzylisoquinoline into (±)-Rhoea Pentanediol

X. The Roche Nutley Conversion of Phthalide Isoquinolines into Rhoeadines

XI. Optical Activity, ORD,CD, and Absolute Configuration

XII. Biogenesis

XIII. Mass Spectroscopy

XIV. UV Spectroscopy

References

Chapter 22. Protostephanine

I. Introduction and Structural Elucidation

II. The Pecherer-Brossi Synthesis of Protostephanine

III. A Suggested Biogenetic Pathway for the Formation of Protostephanine

IV. The Synthesis of Protostephanine by a Route Related to the Biogenetic Pathway

V. The Preparation of Protostephanine Analogs from Thebaine

VI. Pharmacology

VII. UV Spectroscopy

VIII. Erybidine, An Erythrina Alkaloid Related to Protostephanine

References

Chapter 23. Emetine and Related Alkaloids

I. Introduction

II. Chemical Interrelationships between the Ipecac Bases

III. Degradation of Emetine

IV. The Position of the Phenolic Function in Cephaeline

V. Protoemetine

VI. The Stereochemistry of Emetine

VII. Syntheses of Emetine

VIII. Ipecoside, A Monoterpenoidal Isoquinoline Glucoside

IX. Alangiside

X. Biosynthesis

XI. The Partial Synthesis of Secologanin and Ipecoside

XII. Rubremetine Salts

XIII. Pharmacology

XIV. Mass Spectroscopy

XV. NMR Spectroscopy

XVI. UV Spectroscopy

References

Chapter 24. Autumnaline: A Phenethylisoquinoline

I. Introduction

II. Autumnaline

III. Syntheses of Phenethylisoquinolines

IV. Absolute Configuration

V. Biosynthesis

VI. Pharmacology

VII. NMR Spectroscopy

VIII. UV Spectroscopy

References

Chapter 25. Melanthioidine: A Bisphenethylisoquinoline

I. Structural Elucidation of Melanthioidine

II. The Battersby Synthesis of Melanthioidine

III. Enzyme-Induced Syntheses of Analogs of Melanthioidine

References

Chapter 26. The Homoaporphines and Homoproaporphines

I. Three Homoaporphine Alkaloids: Kreysigine, Multifloramine, and Floramultine

II. The Homopro Aporphine Kreysiginone and the Dihydrohomoproaporphine Dihydrokreysiginone

III. Syntheses of Homoaporphines and Homoproaporphines through Phenolic Oxidative Coupling

IV. The Synthesis of Reduced Homoproaporphines through Carbonium Ion Intermediates

V. An Alternate Synthesis of Homoproaporphines through Carbonium Ion Intermediates

VI. Photolytic Syntheses of Homoaporphines and Homoproaporphines

VII. A Photochemical Reaction of Kreysiginone

VIII. Absolute Configuration

IX. Biosynthesis of Homoaporphines

X. Pharmacology

XI. Mass Spectroscopy

XII. NMR Spectroscopy

XIII. UV Spectroscopy

References

Chapter 27. The Homoprotoberberines

I. Synthesis

II. Hydrogenolysis of Homoprotoberberines

III. Absolute Configuration

IV. Mass Spectroscopy

V. NMR Spectroscopy

VI. UV Spectroscopy

References

Chapter 28. The Phenyl Tetrahydroisoquinolines

I. Cryptostyline I

II. X-Ray Analysis and Absolute Configuration

III. Pharmacology

IV. NMR Spectroscopy

V. UV Spectroscopy

References

Chapter 29. The N-Benzyltetrahydroisoquinolines

I. Sendaverine

II. Corgoine

References

Chapter 30. Cherylline

Text

References

Chapter 31. The Naphthalene Isoquinolines

I. Structural Elucidation

II. Biosynthesis

III. NMR Spectroscopy

References

Chapter 32. Addenda

Text

References

Appendix. Occurrence of Isoquinoline Alkaloids by Plant Families

Author Index

Subject Index