Carbohydrate Chem [Splst Period'l Rpt Vol 06]

638 Pages·1973·39.857 MB·English

by  J. Brimacombe

A Specialist Periodical Report
Carbohydrate Chemistry
Volume 6
A Review of the Literature Published
during 1972
Senior Rep0 rter
J. S. Brimacombe, Chemistry Department, University of
Dundee
Reporters
R. J. Ferrier, Victoria University of Wellingfon, New Zealand
R. D. Guthrie, University of Sussex
T. D. Inch, C.D.E.E., Porfon, Wilfs.
J. F. Kennedy, University of Birmingham
R. J. Sturgeon, Heriof- Waff Universify, Edinburgh
@ Copyright 1973
The Chemical Society
Burlington House, London, WIV OBN
ISBN: 0 85186 052 4
Library of Congress Catalog 79-6761
No.
Organic formulae cowiposed by Wright’s Symbolset method
PRINTED IN GREAT BRITAIN BY JOHN WRIGHT AND SONS LTD., AT THE STONEBRIDGE PRESS, BRISTOL
Preface
This Report, the sixth in the series, covers the literature available to us
between mid-January 1972 and mid-January 1973.
A notable feature of these Reports over the past two years has been the
substantial expansion of the material covered in Part 11. Opinions solicited
from a number of readers suggest that the present format, dealing with
monosaccharides etc. and macromolecules under one cover, is generally
the most acceptable and useful. The Reporters would, however, welcome
any suggestions aimed at the improvement of these Reports.
As has been our policy in previous years, Abstracts of the American
Chemical Society Meetings, Dissertation Abstracts, and the patent literature
have not been abstracted. The abbreviation ‘Bn’ is again used throughout
to denote the benzyl group.
We are indebted once again to Professor N. K. Kochetkov for providing
us with English abstracts of a large number of Russian papers and to
Drs. L. W. Doner, N. A. Hughes, and L. C. N. Tucker for reading and
commenting on the whole of Part I. Miss Moira Endersby typed con-
siderable proportions of this Report.
This is the last Report for which we will have the benefit of the expert
reporting of Dr. T. D. Inch. Thanks are due to him for his excellent
contributions to these Reports over the past four years.
April 1973 J. S. B.

Contents
Part I Mono-, Di-, and Tri-saccharides and their Derivatives
1 Introduction 3
2 Free Sugars 5
Isolation and Synthesis 5
Mutarotation and Epimerization 9
Physical Measurements 10
Reactions 12
3 Glycosides 17
0-Glycosides 17
Synthesis 17
Hydrolysis and Related Reactions 22
Other Reactions and Features of Glycosides 24
Natural Products 25
S-Gly cosides 26
C-Glycosides 27
4 Ethers and Anhydro-sugars 30
Ethers 30
Methyl Ethers 30
Substituted Alkyl Ethers 31
Silyl Ethers 33
Intramolecular Ethers (Anhydro-sugars) 33
Epoxides 33
Other Anhydrides 33
5 Acetals 39
Reactions and Properties 39
Acetals Derived from Carbohydrate Hydroxy-groups 40
From Diol Groups on Cyclic Carbohydrates 40
From Diol Groups on Acyclic Carbohydrates 42
From Single Alcoholic Groups 42
6 Esters 44
Carboxylic Esters 44
Carboxylic Orthoesters 47
Phosphates 48
Sulphonates 50
0t her Esters 51
vi Contents
7 Halogenated Sugars 53
Glycosyl Halides 53
0t her Halogenated Derivatives 55
8 Amino-sugars 59
Natural Products 59
Synthesis 59
Physical Properties 63
Reactions 63
Diamino-sugars 64
9 Hydrazones, Osazones, and Related Compounds 67
10 Miscellaneous Nitrogen-containing Compounds 72
Glycosylamines and Related Compounds 72
Nitro-compounds 73
Heterocyclic Derivatives 75
Miscellaneous Compounds 78
11 Thio-sugars 83
12 Derivatives with Nitrogen or Sulphur in the Sugar Ring 86
Nitrogen Derivatives 86
Sulphur Derivatives 87
13 Deoxy-sugars 88
14 Unsaturated Derivatives 91
GI ycals 91
Other Unsaturated Compounds 95
15 Branched-chain Sugars 100
Compounds with an R1-C-ORZ Branch 100
Compounds with an R-C-N Branch 104
Compounds with an R1- C-R* Branch 104
Cyclopropyl Derivatives 110
16 Aldehydo-sugars, Alduloses, Dialduloses, and Diuloses 112
17 Sugar Acids and Lactones 118
Aldonic Acids 118
Aldaric Acids 119
Ulosonic Acids 119
Uronic Acids 119
Ascorbic Acids 122
18 Inorganic Derivatives 123
Carbon-bonded Compounds 123
Oxygen-bonded Coinpounds 123
Contents vii
19 Cyclitols 125
20 Antibiotics 130
21 Nucleosides 137
Synthesis 137
Esters and other Derivatives 141
Nucleosides containing Acyclic Sugars 143
Nucleosides containing Branched-chain Sugar Components 144
C-Nucleosides 144
Anhydronucleosides 146
Reactions 149
Physical Measurements and Conformational Studies 151
22 Oxidation and Reduction 156
Periodate Oxidation 156
DMSO-based Oxidations 156
Electrochemical Procedures 157
Other Oxidations 158
Reduction 160
23 N.M.R. Spectroscopy and Conformational Features of Carbo-
hydrates 163
Furanoid Systems 165
Disaccharides and Polysaccharides 166
Acyclic Derivatives 167
N.M.R. Studies for Establishing the Positions of Substituents 168
Lanthanide Shift Reagents 168
l9FN .M.R. Spectroscopy 169
13C N.M.R. Spectroscopy 169
24 Other Physical Methods 172
I.R. Spectroscopy 172
Mass Spectrometry 172
X-Ray Crystallography 174
25 Polarimetry 177
26 Separatory and Analytical Methods 178
Chromatographic Methods 178
Gas-Liquid Chromatography 178
Column and Ion-exchange Chromatography 178
Paper Chromatography and Electrophoresis 179
Thin-layer Chromatography 179
Other Analytical Methods 179
27 Alditols 181
... Contents
Vlll
Part II Macromolecules
1 Introduction 185
2 General Methods 187
Analysis 187
Structural Meth ods 193
3 Plant and Algal Polysaccharides 197
Starch 197
Cellulose 201
Hemicelluloses 206
Gums-and Pectic Substances 21 8
Pectins 222
Algal Polysaccharides 223
4 Microbial Polysaccharides 228
Bacterial Cell Walls and Membranes 228
Teichoic Acids 228
Pep tidoglycans 235
Lipopol ysaccharides 243
Capsular Polysaccharides and Exopolysaccharides 252
Miscellaneous Polysaccharides 260
Fungal Cell Walls 261
Fungal Exopolysaccharides 269
Miscellaneous Oligo- and Poly-saccharides 270
5 Glycoproteins, Glycopeptides, and Animal Polysaccharides 274
Plant and Algal Glycoproteins 279
Microbial Glycoproteins 28 1
Viral Glycoproteins 283
Haemagglutinins 283
Plant Haemagglutinins 283
Microbial Haemagglutinins 288
Viral Haemagglutinins 289
Animal Haemagglutinins 289
Blood-group Substances 290
Collagens 297
Glycogens 303
Glycosaminoglycuronans, Glycosaminoglycans, and their
Protein and Peptide Derivatives
307
Occurrence, Isolation, Measurement, and Structure 308
General 308
Particular Sources 313
Clinical Conditions
328