Synthesis and reactions of unsaturated sugars.
01 Jan 2003-Advances in Carbohydrate Chemistry and Biochemistry (Adv Carbohydr Chem Biochem)-Vol. 58, pp 55-119
TL;DR: This chapter surveys the chemistry of most of the important types of monosaccharide derivatives that contain single alkene groups—notably, the glycols that are extremely valuable starting materials for a vast range of synthetic transformations.
Abstract: Publisher Summary This chapter discusses the synthesis and reactions of unsaturated sugars. Sugar derivatives that contain double bonds have been developed and used so extensively that they almost certainly constitute the most versatile category of carbohydrate compounds available for use in synthesis of unsaturated sugars. They may be applied both in the synthesis of complex members of the family and of a myriad enantiomerically pure noncarbohydrate compounds—notably, many of interest in medicinal chemistry. In addition, some unsaturated sugar derivatives have themselves been found to possess important therapeutic properties. The unnatural L-nucleoside inhibits reverse transcriptase and shows potent and selective anti-AIDS activity. This chapter surveys the chemistry of most of the important types of monosaccharide derivatives that contain single alkene groups—notably, the glycols that are extremely valuable starting materials for a vast range of synthetic transformations. It also discusses the preparation of the reactions of glycols, elaborates the synthesis of pyranoid and furanoid 2- and 3-Enes, and explains the chemistry of endo-Enes and exo-Enes.
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TL;DR: New principles for the formation of glycoside bonds are discussed and developments, mainly in the last ten years, that have led to significant advances in oligosaccharide and glycoconjugate synthesis have been compiled and are evaluated.
Abstract: Increased understanding of the important roles that oligosaccharides and glycoconjugates play in biological processes has led to a demand for significant amounts of these materials for biological, medicinal, and pharmacological studies. Therefore, tremendous effort has been made to develop new procedures for the synthesis of glycosides, whereby the main focus is often the formation of the glycosidic bonds. Accordingly, quite a few review articles have been published over the past few years on glycoside synthesis; however, most are confined to either a specific type of glycoside or a specific strategy for glycoside synthesis. In this Review, new principles for the formation of glycoside bonds are discussed. Developments, mainly in the last ten years, that have led to significant advances in oligosaccharide and glycoconjugate synthesis have been compiled and are evaluated.
741 citations
TL;DR: This Review summarizes close to 500 primary publications and surveys published since 2000 about the syntheses and diverse bioactivities of C-glycopyranosyl (het)arenes displaying among others antioxidant, antiviral, antibiotic, antiadhesive, cytotoxic, and glycoenzyme inhibitory effects.
Abstract: This Review summarizes close to 500 primary publications and surveys published since 2000 about the syntheses and diverse bioactivities of C-glycopyranosyl (het)arenes. A classification of the preparative routes to these synthetic targets according to methodologies and compound categories is provided. Several of these compounds, regardless of their natural or synthetic origin, display antidiabetic properties due to enzyme inhibition (glycogen phosphorylase, protein tyrosine phosphatase 1B) or by inhibiting renal sodium-dependent glucose cotransporter 2 (SGLT2). The latter class of synthetic inhibitors, very recently approved as antihyperglycemic drugs, opens new perspectives in the pharmacological treatment of type 2 diabetes. Various compounds with the C-glycopyranosyl (het)arene motif were subjected to biological studies displaying among others antioxidant, antiviral, antibiotic, antiadhesive, cytotoxic, and glycoenzyme inhibitory effects.
151 citations
TL;DR: In this article, the authors discuss the role of Oligosaccharide and Glycokonjugate in biologischen systemen, erfordert immer neue and vor allem grosere Mengen dieser Molekule.
Abstract: Die wichtige Rolle, die Oligosaccharide und Glycokonjugate in biologischen Systemen spielen, erfordert immer neue und vor allem grosere Mengen dieser Molekule. Wegen ihrer Heterogenitat in naturlichen Vorkommen wurden und werden grose Anstrengungen unternommen, um die entscheidende glycosidische Bindung sowohl zwischen einzelnen Kohlenhydratresten als auch zu Aglyconen stereoselektiv und in hoher Ausbeute zu erzeugen. Es existieren nun verschiedene Methoden, die effiziente Synthesen von strukturell definierten komplexen Oligosacchariden und Glycokonjugaten ermoglichen.
Das zunehmende Wissen um die bedeutende Rolle, die Oligosaccharide und Glycokonjugate in biologischen Prozessen spielen, hat rasch das Interesse an solchen Verbindungen fur biologische, medizinische und pharmakologische Studien geweckt. Deshalb wurden und werden grose Anstrengungen unternommen, um neue Methoden fur die Synthese von Glycosiden zu entwickeln, wobei das Hauptaugenmerk auf die Bildung der glycosidischen Bindung gerichtet ist. Etliche Ubersichtsartikel wurden in den letzten Jahren zur Glycosidsynthese verfasst, die meisten waren jedoch auf einen bestimmten Typ von Glycosiden oder eine bestimmte Methode zur Glycosidsynthese ausgerichtet. In diesem Aufsatz werden neue Prinzipien fur die Bildung von glycosidischen Bindungen diskutiert, indem vor allem Arbeiten aus den letzten zehn Jahren berucksichtigt werden, die zu erheblichen Fortschritten in der Oligosaccharid- und Glycokonjugatsynthese gefuhrt haben.
148 citations
TL;DR: The report summarizes recent advances in Glycosides of 2-deoxy-sugars, monosaccharides in which the hydroxyl group at C-2 is replaced with a hydrogen atom, with a particular focus on work published since an earlier review on the topic in 2000.
126 citations
TL;DR: A review of recent developments in the use of promoters for the Ferrier rearrangement of O-, N-, C- and S-nucleophiles with glycals can be found in this paper.
121 citations
References
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TL;DR: Two potent inhibitors based on the crystal structure of influenza virus sialidase have been designed and provide an example of the power of rational, computer-assisted drug design, indicating significant progress in the development of a new therapeutic or prophylactic treatment for influenza infection.
Abstract: Two potent inhibitors based on the crystal structure of influenza virus sialidase have been designed. These compounds are effective inhibitors not only of the enzyme, but also of the virus in cell culture and in animal models. The results provide an example of the power of rational, computer-assisted drug design, as well as indicating significant progress in the development of a new therapeutic or prophylactic treatment for influenza infection.
1,778 citations
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TL;DR: This review provides a personal account of the explorations of a research group in oligosaccharide and glycoconjugate construction that led to novel compounds which are in the final stages of preclinical assessment.
Abstract: This review provides a personal account of the explorations of a research group in oligosaccharide and glycoconjugate construction. The journey began twenty years ago with the study of Diels–Alder reactions of complex dienes. By extending this methodology to aldehydo-type heterodienophile equivalents, access to unnatural glycals was gained (LACDAC reaction). From this point a broad-ranging investigation of the use of glycals in the synthesis of oligosaccharides and other glycoconjugates was begun. Mobilization of glycals both as glycosyl donors and glycosyl acceptors led to the strategy of glycal assembly. Several new glycosylation techniques were developed to provide practical underpinning for this logic of glycal assembly. Glycal-based paradigms have been shown to be nicely adaptable to solid phase supported synthesis. Moreover, glycal assembly—both in solution and on solid phases—has been used to gain relatively concise and efficient entry to a variety of biologically interesting and potentially valuable constructs. Some of these syntheses, particularly in the field of tumor antigens, have led to novel compounds which are in the final stages of preclinical assessment. This review presents an account of the chemical reasoning at the center of the program.
594 citations
TL;DR: In this article, a reaction of 3,4,6,tri-O-acetyl-D-galactal with excess ammonium nitrate and sodium azide in acetonitrile produced 2-azido-1-nitrate addition products (53% β-Galacto, 22% α-GalACTo, and 8% α -Ta...
Abstract: Reaction of 3,4,6-tri-O-acetyl-D-galactal with excess ceric ammonium nitrate and sodium azide in acetonitrile produced 2-azido-1-nitrate addition products (53% β-galacto, 22% α-galacto, and 8% α-ta...
584 citations