Royal Society of Chemistry Carbohydrate Chemistry: Volume 28 (Specialist Periodical Reports - Carbohydrate Chemistry)

Carbohydrate Chemistry provides review coverage of all publications relevant to the chemistry of monosaccharides and oligosaccharides in a given year. Excerpt. © Reprinted by permission. All rights reserved. Carbohydrate Chemistry Volume 28 A Review of the Literature Published during 1994 By R. J. Ferrier The Royal Society of Chemistry Copyright © 1996 The Royal Society of Chemistry All rights reserved. ISBN: 978-0-85404-208-1 Contents Chapter 1 Introduction and General Aspects, 1, Chapter 2 Free Sugars, 3, Chapter 3 Glycosides, 19, Chapter 4 Oligosaccharides, 64, Chapter 5 Ethers and Anhydro-sugars, 85, Chapter 6 Acetals, 94, Chapter 7 Esters, 100, Chapter 8 Halogeno-sugars, 115, Chapter 9 Amino-sugars, 120, Chapter 10 Miscellaneous Nitrogen Derivatives, 137, Chapter 11 Thio- and Seleno-sugars, 158, Chapter 12 Deoxy-sugars, 165, Chapter 13 Unsaturated Derivatives, 170, Chapter 14 Branched-chain Sugars, 181, Chapter 15 Aldosuloses and Other Dicarbonyl Compounds, 197, Chapter 16 Sugar Acids and Lactones, 199, Chapter 17 Inorganic Derivatives, 214, Chapter 18 Alditols and Cyclitols, 219, Chapter 19 Antibiotics, 251, Chapter 20 Nucleosides, 263, Chapter 21 N.M.R. Spectroscopy and Conformational Features, 307, Chapter 22 Other Physical Methods, 318, Chapter 23 Separatory and Analytical Methods, 333, Chapter 24 Synthesis of Enantiomerically Pure Non-carbohydrate Compounds, 345, Author Index, 380, CHAPTER 1 Introduction and General Aspects A description of the pioneering work of Emil Fischer in the period around 1890, especially relating to his elucidation of the molecular configuration of glucose and aspects of his philosophical view of chemistry, has appeared. Lemieux and Spohr have looked in detail at how Fischer was led to the "lock and key" concept for enzyme specificity. An animated 386-based PC program with VGA graphics has been produced to assist visualization of the relationship between Fischer and Haworth projections of monosaccharides. An ACS symposium was held in 1993 on the anomeric effect and associated stereoelectronic effects, and as part of it J. T. Edward reviewed the influence of the anomeric effect in carbohydrates covering the origin of its postulation. Several calculations relevant to carbohydrates have been reported. Ab initio M.O. methods have been applied to the axial and equatorial conformations of 2-methoxytetrahydropyrans, and also 2-chloro- and 2-fluoro-tetrahydropyrans, the energy values obtained being found to be dependent on solvent. Force fields have been calculated for monosaccharides and (1 -> 4)-linked polysaccharides, and a review has been written on path energy minimization (PEM), a novel method for generating a reaction path linking two known conformations of molecules. A test example considered the change in pucker angle of α-D-threo-pentulofuranose. The method can identify transition state structures and energy barriers. A major review covering structural and conformational analysis of oligosaccharides of glycoproteins deals with n.m.r., mass spectrometric and molecular modelling methods. Considerable attention has been given in reviews to aspects of synthesis. The question of reactions which are promoted by water has been dealt with covering i) Diels Alder and hetero-Diels Alder reactions by which nionosaccharides may be synthesized; ii) sigmatropic rearrangements of aglycons which lead to asymmetric induction; iii) indium promotion of allylation of aldehydes or ketones and iv) reductive debrominations using soluble tin hydrides and AIBN. A further review has dealt with the hetero-Diels Alder reaction in asymmetric systems, and covered the use of carbohydrate chiral auxiliaries and the construction of pyranose rings from sugar butadien-1-yl ethers. The trichloroacetirnidate method for making glycosides which has become well established as of major importance has been reviewed by the developer, R. R. Schmidt, and the use of aldonolactones in