Fortschritte Der Chemie Organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products

ISBN-13: 9783709171257 / Angielski / Miękka / 2011 / 515 str.

W. Bromer; H. Egge; K. Eiter

Opis

The cyanogenic glycosides, here defined as glycosidic derivatives of iX-hydroxynitriles, represent a rather limited class of natural products, which are widely distributed in the plant kingdom and, to a small ex tent, even in animals. A characteristic feature of these glycosides is their ability to release hydrocyanic acid on treatment with dilute acids or appropriate enzymes. The term "cyanogenic" is used to designate this property, regardless of whether pure substances, plants, or animals, are serving as the source. In the latter cases the term "cyanophoric" is occasionally employed synonymously. Cyanogenesis in plants was probably first discovered by SCHRADER in 1803 (Io3) working with bitter almonds. In 1830, ROBIQUET and BOUTRON-CHARLARD (IOO) succeeded in isolating the parent glycoside, namely amygdalin. Over the years, a total of 18 cyanogenic glycosides have been isolated and characterized more or less completely (Table I, p. 76). It will be noted that the majority of these compounds has been isolated in the era of classical organic chemistry and that progress in .discovering new compounds, not to mention new structural types, has been surprisingly slow. It is worth remembering here that the mechanism .of cyanogenesis has been established only in the minority of known cyanogenic species. The cyanogenic glycosides have last been reviewed in 1958 by DILLE MANN (36). Since then, no complete reviews in this field have appeared. It is the purpose of the present article to survey the more recent ad vances and, hopefully, to stimulate continued interest in these interesting .compounds.

Spis treści

Structural and Biogenetic Relationships of Isoflavonoids.- I. Introduction.- II. Isoflavones.- 1. Simple Isoflavones.- 2. Complex Isoflavones.- 3. Isoflavone Glycosides.- 4. Synthesis of Isoflavones.- III. Isoflavanones.- IV. Rotenoids.- V. Pterocarpans.- 1. Natural Pterocarpans.- 2. Stereochemistry of Pterocarpans.- 3. Reactions and Synthesis of Pterocarpans.- VI. Isoflavans.- VII. 3-Aryl-4-hydroxycoumarins.- 1. Structure Elucidation.- 2. Synthesis of 3-Aryl-4-hydroxycoumarins.- VIII. Coumestans.- 1. Natural Coumestans.- 2. Structure Elucidation and Synthesis.- IX. Other Types of Isoflavonoids.- X. Biogenesis of Isoflavonoids.- 1. 1,2-Aryl Migration as a Common Feature.- 2. Branching Point from the Flavonoid Pathway.- 3. Nature of the Primary Isoflavonoid Product.- 4. Biogenetic Relationships among the Isoflavonoid Classes.- a) Direct Experimental Evidence.- b) Co-occurrence of Classes of Isoflavonoids.- c) Isoflavanones — Dehydropterocarpans — Pterocarpans — Isoflavans — Coumestans.- d) Isoflavones — 2-Hydroxyisoflavones — 3-Aryl-4-hydroxycoumarins.- e) Isoflavones — Rotenoids — Coumaronochromones.- f) Summary of Biogenetic Interrelationships.- References.- Recent Advances in the Chemistry of Cyanogenic Glycosides.- I. Introduction.- II. General Chemical Considerations.- Structural Relationships.- Chemical Properties.- Enzymic Degradation.- III. Detection.- Detection in Fresh Plant Specimens.- Detection on Chromatograms.- IV. Isolation.- Column Chromatography.- Preparative Paper Chromatography.- Preparative Thin Layer Chromatography.- Gas Liquid Chromatography.- V. Structure Elucidation.- Gynocardin.- Triglochinin.- Dhurrin and Taxiphyllin.- Linamarin.- Lotaustralin.- Proteacin.- Nandinaglucoside.- VI. Synthesis.- VII. Distribution.- Cyanogenesis in Higher Plants.- Cyanogenesis in Bacteria.- Cyanogenesis in Fungi.- Cyanogenesis in Animals.- VIII. Biosynthesis.- IX. Metabolic Aspects.- The Fate of Cyanogenic Glycosides in Living Organisms.- Cyanide Metabolism.- References.- Naturstoffe mit Pyridinstruktur und ihre Biosynthese.- Einführung.- I. Natürlich vorkommende Pyridinverbindungen.- 1. Carbonsäuren und einfache Pyridinderivate.- 2. Alkaloide.- a) Nicotin und verwandte Alkaloide.- b) Pyridonalkaloide.- c) Terpenoide Alkaloide.- d) Verschiedenartige Pyridinalkaloide.- 3. Aminosäuren mit Pyridinstruktur.- 4. Mikrobielle Stoffwechselprodukte.- II. Biosynthese des Pyridinringes.- 1. Entstehung der Nicotinsäure.- a) Oxydativer Tryptophanabbau.- b) C3- + C4-Kondensation.- c) Pyridinnucleotid-Cyclus.- 2. Biosynthese von Fusarinsäure und 2,6-Dipicolinsäure.- 3. Lysin als Pyridinvorstufe.- a) Biosynthese von Mimosin sowie Desmosin und Isodesmosin.- b) In vitro-Biosynthese von Anabasin.- 4. Entstehung des Pyridinringes auf dem Monoterpenweg.- 5. Biosynthese der Piericidine A und B.- III. Hypothesen zur Biogenese weiterer Pyridinverbindungen.- Schlußbetrachtung.- Peptide Alkaloids.- I. Introduction.- II. General Properties of Peptide Alkaloids.- III. General Methods and Techniques of Structural Determination.- IV. Structure and Properties of Peptide Alkaloids.- 1. Pandamine.- 2. Zizyphine.- 3. Ceanothine-B.- 4. Scutianine.- 5. Integerrine.- 6. Lunarine.- 7. Homaline.- 8. Adouétine-X.- 9. Americine.- 10. Aralionine.- 11. Ceanothine-A.- 12. Franganine, Frangufoline, and Frangulanine.- 13. Hymenocardine.- 14. Integerrenine and Integerressine.- 15. LBX and LBZ.- 16. Lasiodine-A.- V. Ultraviolet Spectra of Peptide Alkaloids.- VI. NMR Spectra of Peptide Alkaloids.- VII. Mass Spectra of Aryloxy Macrocyclic Peptide Alkaloids.- VIII. Pharmacological Properties of Peptide Alkaloids.- IX. Tables.- 1. Basicity of Peptide Alkaloids.- 2. Peptide Alkaloids.- 3. Sources of Peptide Alkaloids.- References.- Insektensexuallockstoffe.- I. Einleitung.- II. Insektensexuallockstoffe.- a) Olefinische Verbindungen.- b) Aliphatische Verbindungen.- c) Terpenartige Verbindungen.- d) Heterocyclische Verbindungen.- III. Weitere Pheromone.- IV. Insektenhormone.- a) Juvenilhormon (JH).- b) Häutungshormon (MH = moulting-Hormon).- c) Sterilisantien (Juvenilhormonartige Substanzen).- d) Synthetische Produkte.- Arthropod Molting Hormones.- I. Introduction.- II. Hormonal Regulation of Growth of Insects and Crustaceans.- III. Occurrence in Animals.- IV. Occurrence in Plants.- V. Isolation and Assay.- VI. Structure Determination and Chemistry.- 1. ?-Ecdysone (Ecdysone).- 2. ?-Ecdysone (Crustecdysone, 20-Hydroxyecdysone, Ecdysterone).- 3. Tobacco Hornworm Ecdysone III (20,26-Dihydroxyecdysone).- 4. Deoxycrustecdysone.- 5. Ponasterone A.- 6. Ponasterone B.- 7. Ponasterone C.- 8. Inokosterone.- 9. Cyasterone, Isocyasterone, Sengosterone and Capitasterone.- 10. Polypodine B.- 11. Rubrosterone.- 12. Ponasteroside A.- 13. Shidasterone.- 14. Ajugasterone C.- 15. Pterosterone, Makisterone A, Makisterone B, Lemmasterone (Makisterone C, Podecdysone A), Amarasterone A, Makisterone D and Amarasterone B.- 16. Viticosterone E, Stachysterone C, Stachysterone A, Stachysterone B, Podecdysone B and Stachysterone D.- 17. Ajugasterone B.- VII. Synthesis.- 1. ?-Ecdysone.- 2. ?-Ecdysone and Ponasterone A.- 3. Rubrosterone.- 4. Miscellaneous.- VIII. Biosynthesis and Catabolism.- IX. Tables.- 1. Animals Known to Contain Ecdysterols.- 2. Plant Families Containing Ecdysterols.- 3. Plants Known to Contain Ecdysterols.- 4. Properties of Ecdysterols.- 5. NMR Data of some Ecdysterols.- 6. ORD and CD Data of Ecdysterols.- References.- Total Synthesis of Prostaglandins.- I. Introduction.- II. Structure and Chemical Transformations of the Prostaglandins.- III. General Approaches to Prostaglandin Synthesis.- A. Initial Corey Synthesis of dl-PGE1.- B. Corey’s Second Synthesis of dl-PGE1.- C. A Stereocontrolled Synthesis of Prostaglandins E2 and F2? (Corey).- D. Bicyclohexane Route to Prostaglandins.- E. Non-Enzymic Cyclization of Fatty Acids.- IV. Synthetic Routes to Structurally Simplified Prostaglandins.- A. Synthesis of dl-13,14-Dihydro-PGE1, Ethyl Ester.- B. Synthesis of dl-15-Dehydro-PGE1.- C. Synthesis of dl-PGB1.- V. Synthetic Routes to Prostaglandin Analogs.- A. 11-Deoxy-Prostaglandins.- B. 7-Oxa-Prostaglandins.- VI. Miscellaneous Synthetic Approaches.- VII. Resolution of Racemic Prostaglandins.- References.- Chemistry of Cephalosporin Antibiotics.- I. Introduction.- II. Isolation and Structure of Cephalosporin Antibiotics.- A. Historical.- B. Cephalosporin P.- C. Cephalosporin N (Penicillin N).- D. Cephalosporin C.- III. Chemical Transformations of Cephalosporin C.- A. Nomenclature.- B. Sidechain Amido Functions.- 1. Reactions of the 7,? Aminoadipamoyl Group.- 2. Reactions of the 7-Amino Group.- C. Reactions of the ?-Lactam Ring System.- D. Reactions of the Dihydrothiazine Ring System.- 1. Reactions of the Double Bond.- a) Formation of ?2-Isomers.- b) Other Reactions of the Double Bond.- 2. Reactions of the C-3 Substituents.- a) Formation of Desacetyl Derivatives.- b) Nucleophilic Displacement of the Acetate.- c) Hydrogenolysis of the Acetate.- 3. Reactions of the Carboxyl Group.- 4. Formation of Sulfoxides.- E. Conformation of Cephalosporanates.- IV. Physicochemical Properties of Cephalosporanates.- V. Syntheses of Cephalosporins.- A. Total Synthesis.- B. Partial Synthesis.- VI. Biosynthesis.- VII. Biological Activity of Cephalosporanates.- References.- Oligosaccharide der Frauenmilch.- I. Einleitung.- II. Isolierung und Analyse der Oligosaccharide.- 1. Isolierung.- 2. Analytische Methoden.- III. Beschreibung der Zucker.- IV. Vergleich der freien Kohlenhydrate der Milch und des Urins mit den konjugierten Oligosacchariden der Glykosphingolipide.- V. Biosynthese und Blutgruppenmerkmale.- Glucagon: Chemistry and Action.- I. Introduction.- II. Assay.- 1. Physicochemical Methods.- 2. Bioassay.- a) Measurement of the Hyperglycemic Action of Glucagon.- b) Measurement of the Glycogenolytic Effect of Glucagon.- 3. Radioimmune Assays.- III. Chemical Aspects.- 1. Isolation, Properties, and Primary Structure.- 2. Synthesis.- 3. Conformation.- 4. Relationships of Structure and Function.- IV. Site of Formation and Release.- 1. Pancreas.- 2. Intestine.- 3. Release.- V. Glucagon in Blood.- 1. Concentration.- 2. Catabolism.- VI. Glucagon Action.- 1. On Adenyl Cyclase.- 2. In Pancreatic ?-cells.- 3. In Liver.- 4. In Adipose Tissue.- 5. In Heart.- 6. In the Gastrointestinal System.- 7. On Plasma Electrolytes and Renal Function.- VII. Physiologic Role.- References.- Namenverzeichnis. Author Index.- Sachverzeichnis. Subject Index.