The [3,3]-Sigmatropic Allyl Cyanate–Isocyanate Rearrangement on Levoglucosenone Derivatives Stereoselectively Provides 4-Deoxy-4-Aminosugars

Levoglucosenone is a fascinating carbohydrate-based building block obtained from renewable sources, and its use in organic synthesis for the obtainment of highly added-value compounds is particularly encouraged from a circular economy point of view. Herein, the allyl cyanate–isocyanate metal-free rearrangement is reported on the allyl carbamate derived from levoglucosenone. In the presence of O-, N-, and S-nucleophiles this rearrangement forms (4S)-carbamates, ureas, and carbamothioates in a regioand stereoselective manner. The elaboration of the unsaturated adducts through dihydroxylation of the double bond after the rearrangement allows access to new, unique D-allo configured 4-deoxy-4-aminosugar derivatives.