Glucopyranosyl azide synthesis

Strumpel, M K, Buschmann, J, Szilagyi, L, Gyorgydeak, Z, Synthesis and stmctural studies of anomeric 2,3,4,6-tetra-0-acetyl-5-thio-D-glucopyranosyl azides, Carbohydr. Res., 318, 91-97, 1999. 

Z. Gyorgydeak and J. Thiem, Synthesis of methyl (o-glucopyranosyl azide)uronates, Carbohydr. Res, 268 (1995) 85-92. 

Pinter and co-wokers [80] described the synthesis of bicyclic trans-fused glucopyranoso-oxazolidinone 73 and the galacto isomer by reaction of the corresponding glycopyranosyl phosphinimines with carbon dioxide (Scheme 18). A one-pot procedure to prepare 73 from glucopyranosyl azide 70 in high yield (97%) has been described recently [81]. 

In a bimolecular cycloaddition reaction 1-phenylbenzotriazole (369) is obtained from dehydrobenzene (by diazotization of anthranilic acid) and phenyl azide (64joc3733, 6SCB3142). The synthesis of 1-glucosylbenzotriazole from glucosyl azides and dehydrobenzene has been accomplished in this way, 5delding, for example, l-(2,3,4,6-tetra-0-acetyl-j8-D-glucopyranosyl)benzotriazole (370) (68jhc699>. 

Aldehydes, 209 Aldolase, 23, 25, 49,132,383 Alkaline phosphatase, 670 Alkylation, covalent bonding from, 28 Alkyl azides, 80 Allenic steroids, 461-468 Allenic thioesters, 158 Allyl 0-(2-acetamido-3,4,6-tri-0-acetyl-2-deoxy-/3-D-glucopyranosyl) -(1 4) -2-acetamido-3,6-di-0-acetyl-2-deoxy-/3-D-glucopyranoside, synthesis of, 406, 407 Allyl alcohol, 33 Allyl amine, 33... 

The a-l,2-d5-glycosyl azides are synthesized by reaction of 3,4,6-tri-O-acetyl-2-O-trichloroacetyl-p-D-glucopyranosyl chloride (for the synthesis of this compound, see reaction 4.57) with sodium azide in hexamethylphosphoramide (HMPA) at 20°C [59] (reaction 4.55). 

A library of a-D- and P-D-glucopyranosyl triazoles 38-41 have been developed utilizing copper click (Scheme 6.12). An interesting fact observed in this synthesis is that the P-anomeric azide 5 takes 10-45 min to complete the reaction, whereas a-anomeric azide 37 requires 45 -120 min under similar conditions. Difference in reaction rates was correlated with the anomeric effect on the dipole character of the anomeric azides [28]. 

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