1,6‐C‐H and 1,5‐O‐Si Insertion Reactions of Alkylidenecarbene Derivatives of Monosaccharides*

A new protocol has been developed for the generation of alkylidenecarbene derivatives of monosaccharides based on the reaction of trimethylsilylazide and Bu₂SnO with α‐cyanomesylates derived from uloses. When this method is applied to conveniently functionalized carbohydrate derivatives it provides novel heterocyclic ring systems by the rare 1,6‐C‐H or 1,5‐O‐Si insertion reactions.