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

ISBN-13: 9783709186138 / Angielski / Miękka / 2012 / 298 str.

P. a. Cadby; R. G. Cooke; J. M. Edwards

Spis treści

Chemistry of Synthetic Immunomodulant Muramyl Peptides.- I. From Freund’s Adjuvant to MDP.- II. Synthesis of N-acetyl-muramyl-L-alanyl-D-isoglutamine (MDP).- 1. Protected Dipeptide Derivatives.- 2. Protected N-acetyl-muramyl Derivatives.- 3. Coupling of Protected Muramic Acid and Dipeptide Derivatives.- 4. Deprotecting Procedures.- 5. Synthesis of Labelled MDP.- III. Synthesis of Other N-acetyl-muramyl-dipeptides, Analogues and Derivatives of MDP.- 1. Modifications of the Peptide Moiety.- 2. Modifications of the Carbohydrate Moiety.- IV. Synthesis of N-acetyl-muramyl-tri-, tetra-, and -pentapeptides, and of Some Analogs Bearing a Lipophilic Group at the C-terminal End.- 1. Substitution of the ?-amide Group of MDP by a Free or Amidated Amino Acid.- 2. Lengthening of the Peptide Chain at the Carboxyl Function of MDP.- 3. Lipophilic Derivatives of N-acetyl-muramyl-L-alanyl-D-isoglutaminyl-L-alanine.- V. Synthesis of N-acetyl-?-D-glucosaminyl-(1–4)-N-acetyl-muramyl-peptides.- VI. Synthesis of Oligomers and Conjugates of MDP.- 1. Synthesis of Oligomers of MDP.- 2. Synthesis of Conjugates of MDP.- VII. Mass Spectrometry of MDP and Analogues.- VIII. 13C-NMR Spectrometry of MDP and Derivatives.- IX. Analysis of MDP.- Addendum.- References.- Appendix: Leading References on Biological Activities of MDP and Derivatives.- The Chemistry of Longifolene and Its Derivatives..- I. Introduction.- II. Isolation, Occurrence.- III. Structure.- IV. Synthesis.- V. Isolongifolene.- 1. Structure.- 2. Synthesis.- 3. Mechanism of Rearrangement.- VI. Reactions of Longifolene.- 1. “Normal” Reactions.- a) Addition Reactions.- b) Substitution Reactions.- 2. Skeletal Rearrangements.- a) Simple Wagner-Meerwein Rearrangements.- b) Deep-Seated Rearrangements.- 3. Steric Diversion.- a) Electrophilic Additions.- b) Oxidations.- 4. Transannular Reactions.- a) Radical Reactions.- b) Ionic Reactions.- c) Lead Tetraacetate Oxidation of Longifolols.- 5. Conversions into Other Sesquiterpene Skeletons.- 6. Miscellaneous Transformations.- VII. Reactions of Isolongifolene.- 1. Epoxidation and Reactions of Epoxide.- 2. Addition of Halogens and Pseudo-Halogens.- VIII. Ultraviolet Absorption of Some Longifolene Derivatives.- IX. Biosynthesis.- X. Longifolene in Industry.- References.- Homoisoflavanones and Biogenetically Related Compounds..- 1. Introduction.- 2. Isolation and Identification.- 2.1. Isolation.- 2.2. Chromatography.- 3. Structure and Nomenclature.- 3.1. General Aspects and Nomenclature.- 3.2. Ultraviolet-Visible Spectroscopy.- 3.3. Infrared Spectroscopy.- 3.4. Nuclear Magnetic Resonance Spectroscopy.- 3.4.1. 1H-NMR Spectra.- 3.4.2. 13C-NMR Spectra.- 3.5. Mass Spectrometry.- 3.6. Optical Activity and Absolute Configuration.- 4. Chemical Transformations and Syntheses.- 4.1. Synthesis of the Skeleton.- 4.2. Routes to Eucomol.- 4.3. Isomerization and Hydrogenation Reactions of the 3(9)-Double Bond.- 4.4. Deuterium Exchange Reactions.- 4.5. Acylation and Deacylation Reactions.- 4.6. Alkylation and Dealkylation Reactions.- 4.7. Further Reactions of Eucomol.- 4.8. Chemistry of Brazilin and Hematoxylin.- 5. Biosynthesis.- 6. Biological Activity.- 7. Chemotaxonomy.- References.- Naturally Occurring Phenalenones and Related Compounds..- I. Introduction.- II. Phenalenones and Related Metabolites from Fungi.- A. Occurrence.- B. Structure and Chemistry.- C. Synthesis.- D. Biosynthesis.- E. Biological Activity.- III. Phenalenones and Related Metabolites in Higher Plants.- A. Occurrence.- B. Structure Determination.- C. Spectroscopic Methods.- D. Synthesis.- E. Biological Activity.- F. Biosynthesis.- References.- Molecular Mechanisms of Enzyme-Catalyzed Dioxygenation. (An Interdisciplinary Review.).- I. Introduction.- II. Some Basic Chemistry of Molecular Oxygen.- III. Precedents for Metal-Activation of Dioxygen.- 1. How Would an Iron- or Copper-Protein Interact with Molecular Oxygen?.- 2. Precedents for the Transfer of Dioxygen Within the Co-ordination Sphere.- 3. Precedents for the Reaction of Co-ordinated Dioxygen with Free Substrates.- 4. Free Forms of Activated Dioxygen Generated by Metals.- IV. Precedents for Metal Activation of Organic Substrates.- V. The Double Bond-Cleaving Dioxygenases.- 1. Ene-diol Cleaving Dioxygenases.- 2. Extradiol-Cleaving Dioxygenases.- 3. Other Double Bond-Cleaving Dioxygenases.- VI. The Luciferases.- VII. Peroxidizing Dioxygenases.- VIII. Miscellaneous Dioxygenases.- 1. External Flavoprotein Dioxygenases.- 2. Sulfur Oxidizing Dioxygenases.- 3. Inositol Dioxygenase.- 4. Nitropropane Dioxygenase.- 5. Carotene Dioxygenase.- 6. Ribulose Bisphosphate Carboxylate/Oxygenase.- IX. ?-Keto Carboxylic Acid Decarboxylating Dioxygenases.- X. Summary.- Acknowledgments.- References.- Author Index.