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

ISBN-13: 9783709186589 / Angielski / Miękka / 2012 / 376 str.

J. W. Daly; D. Ferreira; S. J. Gould

Opis

The chemistry of condensed tannins has hitherto represented a relatively unattractive and therefore neglected area of study; one in which the weight of research effort involved is invariably disproportionate to the results achieved, in which the participating schools generally confine their approach to specific molecular species, and in which as yet no consensus has been reached regarding likely precursors. The problems which beset those engaged in this field represent a combined function of the abnormal complexity of the gradational range of oligomers of increasing mass and affinity for substrates which typify most extracts rich in tannins, and the consequent problem of their isolation and purification, the high chirality of tannin oligomers, the need to contend with the phenomenon of dynamic 'rotational isomerism about interflavanoid bonds in the IH n.m.r. spectral interpretation of their derivatives, the lack of precise knowledge regarding the points of bonding at nucleophilic centres, and the obvious limitations of a hitherto predominantly analytical approach. The last of these reflects the need for a general method of synthesis which permits unambiguous proof of both structure and absolute configuration also at higher oligomeric levels. With these objectives in mind we initiated a purely synthetic approach based on the premise that flavan-3,4-diols as source of electrophilic flavanyl-4-carbocations, and flavan-3-0Is as nucleophiles (cf 1,2) represent the prime initiators of a process of repetitive condensation in which the immediate products also represent the sequent nucleophilic substrates.

Spis treści

The Metabolism of Gallic Acid and Hexahydroxydiphenic Acid in Higher Plants..- 1. Polyphenol Biosynthesis in Higher Plants — An Overview.- 2. Metabolites of Gallic Acid.- 2.1 Simple Esters — Occurrence and Structural Analysis.- 2.2 Depside Metabolites — Group A.- 2.3 Metabolites Formed by Oxidative Coupling of Galloyl Esters — Groups B and C.- 2.3.1 Hexahydroxydiphenoyl Esters.- 2.3.2 Dehydrohexahydroxydiphenoyl and Isohexahydroxydiphenoyl Esters..- 2.3.3 Hexahydroxydiphenoyl Metabolites — Group B.- 2.3.4 Hexahydroxydiphenoyl Metabolites — Group C.- 3. The Ellagitannins.- 4. Postscript.- References.- The Direct Biomimetic Synthesis, Structure and Absolute Configuration of Angular and Linear Condensed Tannins..- I. Introduction.- II. Bonding Positions at Nucleophilic Centres.- III. Conditions for Interflavanoid Bonding. Stereochemical Course of the Reaction. Chiroptical Method for Determining the Absolute Configuration at C-4.- IV. Direct Biomimetic Synthesis of Biflavanoids.- V. Direct Biomimetic Synthesis of “Angular” Triflavanoids.- VI. Biflavanoids and a “Linear” Triflavanoid with Terminal 3,4-Diol Function.- VII. Composition of the Metabolic Pool and Condensation Aptitudes of Tannin Precursors.- References.- Streptonigrin.- I. Introduction.- II. Isolation and Structure.- III. Structure Activity Relationships and Mechanism of Action.- IV. Biosynthesis.- V. Synthetic Studies.- References.- The Pyrrolizidine Alkaloids.- I. Introduction.- II. The Necine Bases.- 1. Structure and Stereochemistry.- a) 1-Hydroxymethylpyrrolizidines.- b) Pyrrolizidine Diols.- c) Pyrrolizidine Triols.- d) Dihydropyrrolizines.- 2. Synthesis of Necine Bases.- III. The Necic Acids.- 1. C6-Acids — Strigosic Acid.- 2. C8-Acids.- a) (—)-Curassavic Acid.- b) Crispatic Acid and Stereoisomers.- c) Monocrotalic Acid.- d) Latifolic Acid.- e) ?- and ?-Retusanecic Acids.- 3. C9-Acids.- 4. C10-Acids.- a) Retusaminic Acid.- b) Syneilesinolides A-C.- c) Ligularidenecic Acid.- d) Crotaverric Acid.- e) Petasinecic Acid.- f) cis-Nemorensic Acid.- 5. Orchid Acids.- IV. The Pyrrolizidine Alkaloids.- 1. Analytical Methods.- 2. Spectroscopy.- 3. Synthesis.- V. Pyrrolizidine Derivatives in the Lepidoptera.- VI. Biosynthesis.- 1. Necine Bases.- 2. Necic Acids.- VII. Pharmacology.- VIII. Table 1. List of Plant Genera Containing Pyrrolidine Alkaloids.- Table 2. Alkaloid Content of Plant Species Which Have Been Investigated.- Table 3. The Structures of the Pyrrolizidine Alkaloids.- References.- Addendum.- Alkaloids of Neotropical Poison Frogs (Dendrobatidae).- I. Introduction.- II. Batrachotoxins.- A. Structures.- B. Syntheses.- C. Biological Activity.- III. Pumiliotoxin-C Class (cis-decahydroquinolines).- A. Structures.- B. Syntheses.- C. Biological Activity.- IV. Histrionicotoxins.- A. Structures.- B. Syntheses.- C. Biological Activity.- V. Gephyrotoxins.- A. Structures.- B. Syntheses.- C. Biological Activity.- VI. Pumiliotoxin-A Class.- A. Structures.- B. Syntheses.- C. Biological Activity.- VII. Other Alkaloids.- A. Structures, Properties, and Occurrence.- References.- Author Index.