The Isoquinoline Alkaloids Chemistry and Pharmacology

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 ReferencesChapter 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 ReferencesChapter 32. Addenda Text References Appendix. Occurrence of Isoquinoline Alkaloids by Plant FamiliesAuthor Index Subject Index