PREFACE

This 58th volume of Advances continues the sustained theme of definitivearticles written by leaders in the field, providing comprehensive coverageof mature fields or selective treatment of evolving areas. In contrast to thestrong emphasis on glycoconjugates and biological aspects in the precedingVolume 57, the contents of the present issue reflect mainly structural andsynthetic aspects of simpler sugars.

Methodology for glycosidic coupling continues to pose challenges for thesynthetic chemist, and the synthesis of defined oligosaccharide sequencesremains a problem requiring great skill and experimental versatility. Incontrast to the effective and widely available automated procedures basedon solid-support technology for synthesis of oligopeptides and oligonucleo-tides, comparable procedures in the carbohydrate field have been lacking,on account of the complexities of linkage position, anomeric orientation, andprotecting-group manipulation. Among the investigators addressing thisproblem, Seeberger (Cambridge, Massachusetts) and his coworkers Planteand Palmacci have made significant strides in developing the functionalsolid-phase automated synthesizer presented here. It provides practical feasi-bility for synthesis of selected oligosaccharide sequences, although furtherresearch to permit general application for other linkage patterns clearlyremains necessary.

Although sugar derivatives containing unsaturated functionality wereintroduced back in Emil Fischers time, and the rather inappropriate nameglycal became a term that persists to this day, much of their chemistryremained confusing until the advent of NMR spectroscopy. Early surveys inVolumes 7 and 9 of this series, by Freudenberg and Blair respectively, werefollowed notably by Ferriers landmark article in Volume 20, which demon-strated the exceptional versatility of unsaturated sugars in synthesis. Ferrieraugmented his article soon afterwards, in Volume 24. The innovative leader-ship of Ferrier in this area of synthesis has become legendary, and here heand his colleague Hoberg (Lower Hutt, New Zealand) revisit the subject ofunsaturated sugars in a definitive treatment from the current viewpoint.

A comprehensive survey of all classes of internal anhydrides of sugarsis provided in this volume by Cerny (Prague), encompassing cyclic sugarsbridged by three-, four-, and five-membered oxygenated rings. Many suchderivatives offer important potential in synthesis. Earlier articles in thisseries, especially those by Peat in Volume 2 and by Cerny and Stanekin Volume 34, still provide useful background and older detail on thesederivatives, as does the 1972 survey by Guthrie in Volume 1A of TheCarbohydrates, Chemistry and Biochemistry, edited by Pigman andHorton(Academic Press).

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Two related chapters, contributed by de Lederkremer and Marino, andby Varela, both from Buenos Aires, deal with the processes and productsof oxidation of carbohydrates, and offer extensive updating of the 1980article by Green on acids and other oxidation products of sugars, andthe one by Theander on oxidative and degradative reactions of sugarsand polysaccharides, both published in Volume 1B of the PigmanHortontreatise. These two articles from Argentina offer broad coverage of allaspects of carbohydrate oxidation, from both the fundamental view andfrom technological considerations. As an aid to the reader, titles of thecited articles are included in the extensive bibliographic references. Titlesare also incorporated in the references cited in the FerrierHoberg chapter.It is proposed to incorporate such titles on a standard basis in futurevolumes in this series.

The great biological significance of the sialic acids, nine-carbon 5-aminosugars, has long been recognized, and Schauer provided a definitive surveyof their chemistry and biochemistry in Volume 40. Much more recently, thewide occurrence in microorganisms of related nonulosonic acids aminatedalso at position 7 has been demonstrated. Major work on these diaminosugars by three groups has led to the collaborative chapter by Knirel,Shashkov, and Tvetskov (Moscow), Jansson (Huddinge, Sweden), andZahringer (Borstel, Germany) featured here as the last contribution to thisvolume.

The life and work of one of the greatest carbohydrate scientists of ourtime, Raymond U. Lemieux, is recalled here in a sensitive account by Bundle(Edmonton). During a remarkably productive career extending over morethan half a century, Lemieux pioneered the application of NMR spectros-copy in chemistry, developed rational approaches for glycosidic coupling,made major contributions to our understanding of three-dimensionalcarbohydrate structures and protein binding, and made importantcontributions in the biomedical area. His own articles in these Advancesinclude the chemistry of streptomycin in Volume 3, the mechanisms ofreplacement reactions in Volume 9, and in Volume 50 a consideration ofEmil Fischers lock and key concept of enzyme specificity.

With this present volume we welcome Peter H. Seeberger and YuriyKnirel to the Board of Advisors.

Washington, DC DEREK HORTONAugust 2003

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Preface