Glycosylidene Carbenes a new approach to glycoside synthesis. Part 1. Preparation of glycosylidene‐derived diaziridines and diazirines

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Abstract
A new approach towards the synthesis of glycosides based upon a (formal) insertion of glycosylidene carbenes into OH bonds is presented. The synthesis and characterization of the glycosylidene‐derived diazirines 25–28, precursors of glycosylidene carbenes, are described. The diazirines were prepared by the rapid, high‐yielding oxidation of the diaziridines 20 and 22–24 with I2/Et3N. The diaziridines, the first examples of C‐ alkoxy‐diaziridines, were formed in high yields by the reaction of the [(glycosylidene)‐amino]methanesulfonates 14 and 17–19 with a saturated solution of NH3 in MeOH. The diazirines are highly reactive compounds, losing N2 at room temperature or below. The reaction of the gluco‐configurated diazirine 25 with i‐PrOH yielding a mixture of the α‐ and β‐D‐glucosides 29 and 30 illustrates the potential of glycosylidene‐derived diazirines as a new type of glycosyl donors.