Carbohydrate Chemistry provides review coverage of all publications relevant to the chemistry of monosaccharides and oligosaccharides in a given year. The amount of research in this field appearing in the organic chemical literature is increasing because of the enhanced importance of the subject, especially in areas of medicinal chemistry and biology. In no part of the field is this more apparent than in the synthesis of oligosaccharides required by scientists working in glycobiology. Clycomedicinal chemistry and its reliance on carbohydrate synthesis is now very well established, for example, by the preparation of specific carbohydrate- based antigens, especially cancer-specific oligosaccharides and glycoconjugates. Coverage of topics such as nucleosides, amino-sugars, alditols and cyclitols also covers much research of relevance to biological and medicinal chemistry. Each volume of the series brings together references to all published work in given areas of the subject and serves as a comprehensive database for the active research chemist Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading authorities in the relevant subject areas, the series creates a unique service for the active research chemist, with regular, in-depth accounts of progress in particular fields of chemistry. Subject coverage within different volumes of a given title is similar and publication is on an annual or biennial basis.
Carbohydrate Chemistry Volume 12
A Review of the Literature Published during 1978
By J. F. Kennedy, N. R. WilliamsThe Royal Society of Chemistry
Copyright © 1981 The Royal Society of Chemistry
All rights reserved.
ISBN: 978-0-85186-940-7Contents
Part I Mono-, Di-, and Tri-saccharides and their Derivatives,
1 Introduction, 3,
2 Free Sugars, 4,
3 Glycosides, 15,
4 Ethers and Anhydro-sugars, 37,
5 Acetals, 47,
6 Esters, 51,
7 Halogenated Sugars, 65,
8 Amino-sugars, 70,
9 Miscellaneous Nitrogen Derivatives, 82,
10 Thio-, Seleno-, and Phosphoro-sugars, 92,
11 Deoxy-sugars, 99,
12 Unsaturated Derivatives, 104,
13 Branched-chain Sugars, 112,
14 Aldosuloses, Dialdoses, and Diuloses, 122,
15 Sugar Acids and Lactones, 128,
16 Inorganic Derivatives, 136,
17 Alditols and Cyclitols, 139,
18 Antibiotics, 146,
19 Nucleosides, 156,
20 N.M.R. Spectroscopy and Conformational Features, 187,
21 Other Physical Methods, 198,
22 Separatory and Analytical Methods, 207,
23 The Synthesis of Optically Active Non-carbohydrate Compounds, 209,
Part II Macromolecules,
1 Introduction, 215,
2 General Methods By R. J. Sturgeon, 221,
3 Plant and Algal Polysaccharides By I. M. Morrison, 231,
4 Microbial Polysaccharides By R. J. Sturgeon, 257,
5 Glycoproteins, Glycopeptides, Proteoglycans, and Animal Polysaccharides By R. J. Sturgeon, 287,
6 Enzymes By J. F. Kennedy, 374,
7 Glycolipids and Gangliosides By I. M. Morrison, 484,
8 Chemical Synthesis and Modification of Oligosaccharides Polysaccharides, Glycoproteins, Glycopeptides, and Glycolipids By C. M. Sturgeon, 505,
Author Index, 592,
CHAPTER 1
Part I MONO-, DI-, AND TRI-SACCHARIDES AND THEIR DERIVATIVES
By B. E. Davison R. J. Ferrier N. R. Williams
1 Introduction
The general terms of reference remain the same as for previous volumes in this series. In order to minimize the time required for editorial collation, the previous system of numbering diagrams and references sequentially throughout Part I has been discarded in favour of each chapter carrying its own set of diagram and reference numbers as in Part II. We hope this alteration will not detract too seriously from the usefulness of the report. We have attempted to maintain the previous policy of providing a generous system of cross-references between chapters.
More than one thousand references quoted in Part I clearly reflect the continued high level of interest in the chemistry of carbohydrates, and the report demonstrates the particular interest now being shown in the synthesis of natural and analogous glycosides and disaccharides (Chapter 3), carbohydrate antibiotics (Chapter 18), and of course nucleosides (Chapter 19), which together account for over one-third of all the references cited.
Texts published this year of general interest to carbohydrate chemists have included issues in the Advances in Carbohydrate Chemistry and Biochemistry series, which are prefaced by appreciations of the late Professors E. J. Bourne and E. L. Hirst; these texts include review articles on 1,6-anhydro sugars, cyclic acetals of aldoses and aldosides, the Koenigs-Knorr reaction, carbohydrate boronates, and the biosynthesis of sugars in antibiotics. Extensive surveys of carbohydrate derivatives are also included in several books devoted to antibiotics.
2 Free Sugars
A review of aspects of the structure and reactivity of carbohydrates has appeared. The free-radical telomerization of vinylene carbonate (1,3-dioxal-2-one) with polyhalomethanes has been dealt with in a review; telomers so derived may be converted to aldoses containing from three to eight carbon atoms (see below). Ab initio SCF calculations have been used to predict the electron distribution, the electrostatic molecular potential around the oxygens, and the hydration and cation binding schemes of C3-endo-gg-ribose. The latter were correlated with recent experimental results.
1 Isolation and Synthesis
Melibiose, raffinose, glucose, and fructose were detected in developing rice (strain IR29), whereas in strain IR28 sucrose, glucose, fructose, raffinose, maltose, melibiose, glucodifructose, maltotriose, and higher oligosaccharides were found. More free sugars were present in the developing grain than when it was mature. Bran contains a higher proportion of raffinose and fructose than does milled rice. The free sugars, water-soluble gums, and hemicelluloses present in barley grains were compared before and after malting. Sugars detected were arabinose, xylose, galactose, glucose, fructose, maltose, and sucrose, levels of which increase on malting. The hydrolysate of the extracellular polysaccharides of Rhizobium (strain CB756) was shown to contain 6-deoxy-L-talose, 3-O-methyl-D-glucose, and 6-O-methyl-D-galactose. D-Gal-actofuranose was found to be present in the capsular polysaccharide of Klebsiella serotype K41.
Per-C-deuteriated D-glucose has been synthesized using the sequence shown in Scheme 1. A simple synthesis of L-idose from (1) by sequential treatment with sodium borohydride, sodium methoxide, and acid has been reported. Also prepared were L-idose di(ethylthio)acetal and 1-deoxy-L-iditol.
The polymerization of formaldehyde has been studied using various catalysts and complexing co-catalysts. When a bed of NaX-zeolite spheres was used, aqueous formaldehyde at 95 °C gave an initial conversion to formose sugars of 50% at pH 5 — 7. Rapid irreversible catalyst deactivation then occurred due to the presence of formic acid produced in the undesired Cannizaro reaction. The problem was overcome by incorporation of 0.86 cm3 sodium hydroxide per cm3 formaldehyde into the combined feed to the reactor thus maintaining pH 10 — 12. Conversion only fell from 95% to 92% during 3 h. Catalysts suitable for use in homogeneous polymerization were prepared from calcium hydroxide and glucose or dihydroxyacetone, and their physical and chemical properties were investigated. ESCA and i.r. analysis suggest a loosely structured dynamic mixture of species derived by co-ordination between the alkaline earth hydroxide and the hydroxylated compound. When the catalyst was used with formaldehyde in 2H2O no C — 2H bonds were formed, showing that water does not participate in the formose reaction and that the latter occurs within the complex. When glucose was used as the complexing co-catalyst with calcium hydroxide in a tank reaction, the Canni-zaro reaction was reduced to ~ 2% with near-complete conversion to formose sugars. Although calcium hydroxide is a good catalyst for the Cannizaro reaction, the calcium hydroxide-glucose complex is not.
Cold-plasma decomposition of methane–water mixtures produced simple organic compounds containing formaldehyde; on apatite surfaces under u. v. irradiation and at various pH values erythrose, ribose, glucose, glucuronic acid, and cellobiose were obtained. Ammonia was found to favour the synthesis of sugars when used to create alkaline media. (The authors report all these sugars as D-enantiomers but no evidence for optical purity is presented.)
The octodiose present in apramycin has been prepared as its di-isopropyl-idene-monobenzyl derivative (2), using the synthesis shown in Scheme 2.
Oxidation of 1,2:4,5-di-O-isopropylidene-D-xylitol, which is produced together with the...
