Carbohydrate Chemistry Volume 2

308 Pages·1969·23.756 MB·English

A Specialist Periodical Report
Carbohydrate Chemistry
Volume 1
A Review of the Literature Published
during 1967
Senior Reporter
R. D. Guthrie, University of Sussex, Brighton, Sussex
Rep0 rters
R. J. Ferrier and M. J. How
@ Copyright 1968
The Chemical Society
Burlington House, London, WIV QBN.
Organic formulae composed by Wright’s Symbolset method
PRINTED IN GREAT BRITAIN BY JOHN WRIGHT AND SONS LTD., AT THE STONEBRIDGE PRESS, BRISTOL
Preface
It has been our aim in preparing this first Report to outline and correlate
the majority of papers published in the field of carbohydrate chemistry
during 1967. The terms of reference taken for Parts I and I1 itre set out
in the respective Introductions and emphasise the chemical rather than the
biochemical aspects of the subject; to this extent therefore the coverage is
selective. We would point out that the nucleoside section in particular is
less than complete. We hope, however, to have produced a review from
which the development of carbohydrate chemistry during the year can be
followed in some detail.
Work available to the authors up to midJanuary 1968 has been included.
Papers which appeared in 1967 journals and which became available after
that date will be covered in the Report for 1968, and the Reviewers will be
glad to consider any 1967 papers which authors feel should have been
included in this first issue. Research described in Abstracts of the American
Chemical Society Meetings or Diss. Abs. was not abstracted.
Comments and advice which will enable subsequent Reports to be
brought into line with the precise requirements of research chemists are
invited.
We thank Dr. E. Mukrnenev for help with the translation of Russian
papers.
R. D. G.
R. J. F.
M. J. H.
April 1968.

Contents
Part I Mono-, Di-, and Tri-saccharides
and their Derivatives
.
1 Introduction 3
.
2 Free Sugars 5
Isolation and Synthesis . 5
Mut ar ot at ion 6
Physical Measurements . 7
.
Reactions 8
3 Glycosides . . 12
0-Glycosides . . 12
Synthesis . . 12
Hydrolysis and Anomerisation . . 19
Other Reactions . 24
Natural Products . . 27
S-Glycosides . . 28
C-Glycosides . . 30
Other Aspects of Glycoside Chemistry . . 32
. .
4 Ethers and Anhydro-sugars 34
Ethers . . 34
Methyl Ethers . . 34
Substituted Alkyl Ethers . . 36
. .
Trimethylsilyl Ethers 38
.
Intramolecular Ethers (Anhydro-sugars) . 38
. .
Epoxides 38
Other Anhydrides . . 41
5 Acetals . . 44
Acetals Derived from Carbohydrate Carbonyl Groups . 44
Acetals Derived from Carbohydrate Hydroxy-groups . . 46
From Diols on Acyclic Carbohydrates , . 46
From Diols on Cyclic Carbohydrates . . 47
From Single Alcoholic Groups . . 51
6 Esters . . 52
Acetates . . 52
Substituted Acetates and Other Nonaromatic Carboxylates 54
. .
Benzoates 56
Carboxylic Orthoesters . . 58
Carbonates . . 59
Thiocarbonates . . 61
vi Contents
Phosphates . 63
Sugar Phosphates . 64
Nucleoside Phosphates and Phosphites . 65
Sulphates . 67
Sulphonates . 68
Synthesis . 68
Displacement Reactions without Participation . 68
Displacement Reactions with Participation . 72
Displacement Reactions Accompanied by Rearrangement 78
Reactions of Nitrobenzene-p-sulphonates 80
,
Nitrates 82
Borates and Boronates . 82
7 Halogenated Sugars . 83
Glycosyl Halides . 83
Other Halogenated Derivatives . 85
8 Amino-sugars . 87
Naturally occurring Compounds . 87
Synthesis . 88
Reactions . 92
Physical Measurements . 98
Diamino- and Polyamino-sugars . 99
.
9 Hydrazones, Osazones, and Formazans 101
10 Miscellaneous Nitrogen-containing Compounds . 105
Glycosylamines . 105
Glycosylurea Derivatives . 106
Azides . 106
Nitro-compounds . 107
Other Nitrogen-containing Compounds . 110
.
11 Thio-sugars 114
12 Derivatives with Sulphur, Selenium, or Nitrogen in the Sugar Ring 116
Sulphur Derivatives . 116
Selenium Derivatives . 117
Nitrogen Derivatives . 118
.
13 Deoxy-sugars 121
14 Unsaturated Derivatives . 126
Glycals . 126
Other Unsaturated Compounds . 129
15 Branched-chain Sugars 135
.
16 Alduloses and Diuloses 138
17 Sugar Acids and Lactones . 142
Aldonic Acids . 143
Uronic Acids. 145
Saccharinic Acids . 146
Ascorbic Acid . 147
Contents vii
18 Inorganic Derivatives . 148
Carbon-bonded Compounds . 148
Oxygen-bonded Compounds . 149
19 Cyclitols . 152
Amino-cyclitols . 157
20 Antibiotics . 162
21 Nucleosides . 167
Naturally occurring Nucleosides 167
Synthesis . 167
Esters . 170
Other Nucleoside Derivatives . 170
22 Oxidation and Reduction . 172
Periodate Oxidation . 172
Platinum-catalysed Oxidation . 174
DMSO-based Oxidations 175
Other Oxidations . 175
Reduction . 178
23 N.m.r. Spectroscopy and Conformational Features of Carbo-
hydrates . 180
.
24 Other Physical Methods 186
1.r. Spectroscopy . 186
Mass Spectrometry 186
X-ray Crystallography . 187
E.s.r. Spectroscopy 188
.
25 Polarimetry 189
26 Separatory and Analytical Methods . 191
Chromatographic and Related Methods . 191
Gas-liquid Chromatography . 191
Column Adsorption Chromatography . 192
Paper and Thin-layer Chromatography . 192
Ion-exchange Chromatography . 195
Electrophoresis . 195
Other Analytical Methods . 196
27 Alditols . 199
Part II Macromolecules
Introduction . . 203
.
General Methods 204
Analysis. . . 204
.
Structural Methods 205
Specific Interactions of Carbohydrates with Concaiiavalin A 207
Plant Polysaccharides . . 209
viii Contents
4 Bacterial Polysaccharides . 220
Bacterial Cell-walls . 230
Fungal Polysaccharides . 236
.
5 Glycoproteins and Glycopeptides 240
Carbohydrate-pepticle Linkages . 240
Plant Glycoproteins . 242
Mammalian Glycoproteins . 242
.
Collagen 242
Bone . 242
Brain . 243
Aorta 243
Submaxillary Gland . 243
Serum Glycoproteins . 244
a,- and a,-Acid Glycoproteins . 246
.
Blood-group Substances 248
Miscellaneous Glycoproteins . 252
6 Carbohydrate Sulphates . 254
.
Polysaccharide Sulphates from Animal Tissues 254
Structural Studies . 257
Molecular Architecture of Glycosaminoglycan-proteins in
Animal Tissues . 262
Biosynthesis of Sulphated Glycosaminoglycans . 264
Other Sulphated Glycosaminoglycans . 266
Polysaccharide Sulphates and Other Polysaccharides from
Seaweeds 267
.
Agar 269
.
Laminarin 270
Fucoidan . 270
Alginic Acid . 270
Oxidative-reductive Depolymerisation of Alginate, Hyaluro-
nate, and Other Polysaccharides . 27 1
7 Miscellaneous Polysaccharides . 273
.
8 Chemical Synthesis and Modification of Polysaccharides 274
.
9 Physicochemical Studies 278
10 Glycolipids 280
Index of Authors . 283