A process for the de novo synthesis of imino‐C‐glycosides is described. The methodology is based on the reaction of 1‐C‐stannylated iminosugars with various electrophiles under the conditions of Migita‐Kosugi‐Stille cross‐couplings, which gives 1‐C‐substituted iminosugar derivatives in a stereoretentive process. The required iminoglycosyl stannanes are obtained by way of the highly stereoselective addition of tributylstannyllithium to (SR)‐ or (SS)‐N‐tert‐butanesulfinyl glycosylamines, followed by an activation cyclization sequence. Most interestingly, the methodology is tunable: the configuration of the tin adduct is controlled exclusively by the tert‐butanesulfinyl auxiliary, thus giving access after ring formation to ‘α’‐configured or ‘β’‐configured iminoglycosyl stannanes. With the subsequent stereoretentive C−C bond‐forming process, the methodology allows the synthesis of pseudo anomers of imino‐C‐glycosyl compounds in a controlled fashion.

The convenient and straightforward preparation of dideoxy-1,4-and 1,5-iminopentitol derivatives from protected sugar hemiacetals by way of N-tert-butanesulfinyl glycosylamines and open-chain aminoalditols is reported. The synthetic procedure is a method of choice for the making of these important scaffolds of biological interest.

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