Displacement reactions of a 1,2-anhydro-α-d-hexopyranose: installation of useful functionality at the anomeric carbon

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.

Synthesis and reactions of unsaturated sugars.

Glycosylimidate, 16. Synthese des Trisaccharids aus der „Repeating Unit”︁ des Kapselpolysaccharids von Neisseria meningitidis (Serogruppe L)

Preparation of pyranoid glycal derivatives from phenyl thioglycosides and glycosyl phenyl sulphones

Human tumours are often marked by the expression of unusual carbohydrate structural motifs. These carbohydrate domains are manifested as cell-surface bound glycolipids or glycoproteins. This raises the possibility of using cell-free equivalents of these domain compounds, obtained by total synthesis with a view towards triggering some level of immune response. In fact, the serum of mice immunized with fully synthetic compounds that mimic cell-surface tumour antigens has already been shown to recognize pertinent human cancer cell lines. Further advances in this field depend critically on the availability of these tumour-associated carbohydrate antigens which cannot be readily isolated from natural sources in sufficient quantities. Here we present the successful total synthesis of an adenocarcinoma antigen, KH-1, and of a bioconjugatable analogue which can bind to a carrier protein. These results illustrate the capabilities of oligosaccharide synthesis for reconstructing the challenging structural motifs characteristic of carbohydrate antigens, and thereby open up new possibilities for the development of anticancer vaccines.

Total synthesis of the potential anticancer vaccine KH-1 adenocarcinoma antigen

Three fluoro-substituted unsaturated sugars have been synthesized by transformations within the D-glucal and ethyl 2,3-dideoxy-α-D-erythro-hex-2-enopyranoside series. A number of the intermediate unsaturated sugars not previously described have been characterized. The advantages of the t-butyldimethylsilyl blocking group in such syntheses are described.

Studies on unsaturated sugars with particular reference to the synthesis of 6-Deoxy-6-fluoro derivatives

Repetition of a published method for the alleged synthesis of cyclohexane-1,3/2-triol showed that the product was in fact the 1,2/3 isomer. A new synthesis of the 1,3/2 compound is described.

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Peter M. Fredericks

Papers

Studies on unsaturated sugars with particular reference to the synthesis of 6-Deoxy-6-fluoro derivatives

Synthesis of Cyclohexane-1,3/2-triol

Synthesis of cyclohexane-1,3/2-triol

Studies on unsaturated sugars with particular reference to the synthesis of 6-deoxy-6-fluoro derivatives