5-Thio-D-glucal

The 5-thio analog of A -acetyl-D-glucosamine 50 was synthesized from suitably protected furanoid [98-100] or open-chain [101] D-glucosamine derivatives employing the general approach via the thiirane route [102], as well as from 5-thio-D-glucal 51 [103] via azidonitration [104]. 

Csuk, R, Glanzer, B I, A short synthesis of 2-acetamido-2-deoxy-5-thio-D-glucose and -D-mannose from 5-thio-D-glucal, J. Chem. Soc. Chem. Commun., 343-344, 1986. 

Korytnyk, W, Angelino, N, Dodson-Simmons, O, Hanchak, M, Madson, M, Valentekovic-Horvath, S, Synthesis and conformation of 5-thio-D-glucal, an inhibitor of glycosidases, Carbohydr. Res., 113, 166-171, 1983. 

In a different synthesis of 1,5-anhydrohexitols from a compound having a pyranoid ring, Lehmann and Friebolin31 treated 1,5-anhydro-2-deoxy-D-arafemo-hex-l-enitol (D-glucal) (20) with a-toluenethiol in the presence of light, and obtained l,5-anhydro-2-S-benzyl-2-thio-D-mannitol (21) and the epimeric anhydro-D-glucitol in equal amounts. 

Scheme 5 shows the synthesis of 6-sulphono-a-D-glucopyranose 1-phosphate from the appropriately protected a-D-glucose 1-phosphate (13) via the disulphide (14). The product was isolated as the tris-cyclohexylammonium salt (15). A convenient route to 6-thio derivatives of D-glucal from D-glucose is referred to in Chapter 13. 

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