Carbohydrate Chemistry provides review coverage of all publications relevant to the chemistry of monosaccharides and oligosaccharides in a given year.
Carbohydrate Chemistry Volume 13
A Review of the Literature Published during 1979
By J. F. Kennedy, N. R. WilliamsThe Royal Society of Chemistry
Copyright © 1982 The Royal Society of Chemistry
All rights reserved.
ISBN: 978-0-85186-112-8Contents
Part I Mono-, Di-, and Tri-saccharides and their Derivatives,
1 Introduction, 3,
2 Free Sugars, 4,
3 Glycosides, 17,
4 Ethers and Anhydro-sugars, 44,
5 Acetals and Ketals, 53,
6 Esters, 57,
7 Halogeno-sugars, 73,
8 Amino-sugars, 78,
9 Miscellaneous Nitrogen Derivatives, 89,
10 Thio- and Phosphoro-sugars, 101,
11 Deoxy-sugars, 107,
12 Unsaturated Derivatives, 113,
13 Branched-chain Sugars, 123,
14 Dicarbonyl Compounds and their Derivatives, 131,
15 Sugar Acids and Lactones, 136,
16 Inorganic Derivatives, 145,
17 Alditols and Cyclitols, 150,
18 Antibiotics, 157,
19 Nucleosides, 173,
20 N.m.r. Spectroscopy and Conformational Features, 199,
21 Other Physical Methods, 214,
22 Separatory and Analytical, 223,
23 Stereospecific Syntheses from Carbohydrates, 227,
Part II Macromolecules,
1 Introduction, 233,
2 General Methods, 237,
3 Plant and Algal Polysaccharides, 247,
4 Microbial Polysaccharides, 274,
5 Glycoproteins, Glycopeptides, and Animal Polysaccharides, 313,
6 Enzymes, 417,
7 Glycolipids and Gangliosides, 544,
8 Chemical Synthesis and Modification of Oligosaccharides Polysaccharides, Glycoproteins, Enzymes, and Glycolipids, 572,
Author Index, 705,
CHAPTER 1
Introduction
Interest in the chemistry of mono- and di-saccharides continues unabated, with nearly 1300 references being mentioned in Part I of this report. Glycosides alone account for nearly 200 references, in part reflecting both the expanding range of glycosidic natural products being discovered, and the increasing study of di- and tri-saccharides following the advent in recent years of several efficient methods for the synthesis of α-glycosides. Likewise the range of complex carbohydrate-containing antibiotics shows no signs of reaching a limit, posing fresh challenges to synthesis which chemists have eagerly accepted; two elegant syntheses of spectinomycin are reported in Chapter 18. There is also great interest being shown in glucose as a convenient asymmetric source material for the synthesis of a wide range of chiral natural products, which is reflected in Chapter 23.
A text on aspects of asymmetry in carbohydrates has appeared, which includes reviews on the composition of reducing sugars in solution, asymmetric reactions of carbohydrates containing carbonyl groups, and prochirality and pseudoasymmetry in carbohydrate biochemistry, besides articles on nitro-sugar stereochemistry, chiral sulphur derivatives, and carbohydrate crown-ether compounds. A general survey of organic chemistry includes an extensive account of monosaccharide chemistry.
The latest issue in the series 'Advances in Carbohydrate Chemistry and Biochemistry' contains appreciations of the late Professors J. A. Mills and J. V. Karabinos, and includes a review on the chemistry of glycosiduronic acids.
CHAPTER 2
Free Sugars
The composition of reducing sugars in aqueous solution has been surveyed. A review on the structural properties of the anomeric centre in pyranoses and pyranosides has appeared. Three reviews concerning properties of fructose have been published, dealing with its metabolism, its chemical structure and properties, and its chemistry with some emphasis on the relationship between molecular structure and calculated and experimental values of optical activity, and such properties as taste. The production of nutritive sweeteners by acidic and enzymic hydrolysis of starch has been reviewed.
1 Isolation and Synthesis
Analyses by t.l.c. and g.l.c. of honeys from Robinia spp. and honeydew have shown that the former contains evlose and the latter melezitose as well as the usual mono- and di-saccharides. 3-Deoxytetrulose, useful for synthesis of 2-hydroxybutanoic acid, has been isolated in 4% yield from sodium bicarbonate treatment of xylan. Incubation of Aspergillus fumigatus with inulin produces di-D-fructofuranose 1,2': 2,1'-dianhydride. An improved method for the preparation of crystalline β-lactose from heating a supersaturated solution of α-lactose hydrate has been reported. Differential scanning calorimetry was used to determine its true melting point. Improved yields of β-lactose have also been claimed from treatment of α-lactose hydrate with 0.02% sodium hydroxide in alcohols for 2 h. Methanol gave the best yields provided water content was below 10%.11 A blue-green alga, Agmenellum quadruplicatum, has been used to prepare 13C-labelled D-glucose, 2-O-α-D-glucosyl glycerol, 2-O-α-D-glucosyl glyceric acid, and sucrose by photobiosynthesis from 20 mole % 13CO2 as carbon foodstock.
A further paper on the cold-plasma decomposition of methane-water mixtures in the presence of apatite has appeared (see vol. 12, p. 6). Glucose 6-phosphate and ribose 5-phosphate were found among the products.
Reports on further studies of the formose reaction continue to appear. An investigation of solid catalysts has shown that selectivity can be achieved using a tobermorite or calcium oxalate; the major products were branched-chain sugar alcohols, 2-hydroxymethylglycerol, and 2,4-bis(hydroxymethyl)- and 3-hydroxy-methyl-pentitol. The same group has studied the effect of different solvent systems on the reaction. The calcium oxide-catalysed reaction was found to require a hydroxylic solvent and the induction period was shown to be related to the concentration of dissolved Ca2+ ion. The reaction in 90% and 100% methanol was analysed in detail; the formation of formaldehyde hemiacetal was shown to be essential, and competition between the Cannizzaro reactions and sugar formation was the important factor affecting sugar yield. High temperatures have been shown to produce hexoses from formaldehyde-calcium hydroxide. At 98°C the induction period was 15 s and the reaction gave 84% hexoses at 18% formaldehyde conversion, of which 90% was glucose. No branched-chain sugars were detected. Conversion was complete within 3 min. Higher conversions or lower temperatures gave more complex mixtures. The calcium hydroxide-catalysed reaction has been studied to determine the effects of pH and catalyst-formaldehyde ratio; a greater proportion of carbohydrate is produced when the latter is higher. With lower catalyst concentrations Cannizzaro products become dominant. Three 2-deoxy-sugars were formed in a one-step crossed formose reaction of acetaldehyde and formaldehyde.
High performance liquid chromatography has been used to study the mechanism and kinetics of the formose reaction. The mechanism proposed is shown in Scheme 1. Previous emphasis on mixed aldol condensations between C2 and C3 fragments is not supported, these providing only minor pathways.
The Fischer-Kiliani synthesis has been used to prepare 13C-enriched carbohydrates. The nitriles formed using Na 13CN were reduced over Pd-BaSO4 at pH 4.2 and 25 °C to give pentoses and hexoses in 60-90% yield. 1-Amino-1-deoxyalditols were produced in ~10% yield and their formation was favoured when hemiacetal formation was hindered in the parent aldoses. Preparation of glycolaldehyde, glyceraldehyde, erythrose, and threose with 13C-enrichment at various specific positions for use in...
