Application of the triisobutylaluminum‐promoted reductive rearrangement to sucrose‐5‐enes

Abstract

AbstractCarbohydrate‐based vinyl acetals (5‐hex‐enopyranosides) undergo reductive rearrangement with triisobutylaluminum (TIBAL) to afford highly functionalized cyclohexanes in which both the aglycon and anomeric stereochemistry are retained. Here, we report the first application of this process to the rearrangement of hex‐5‐enopyranosides of sucrose in which the interglycosidic oxygen atom of the vinyl acetal system links the anomeric centers of both monosaccharide units. The sucrose‐derived 5‐hex‐enopyranoside 1 undergoes smooth reductive rearrangement with TIBAL to afford the (1 → 2′) ether‐linked pseudo‐disaccharide 2 in 34% yield. The rearrangement is accompanied by some loss of stereochemical integrity at C‐2′ due to a competitive exo‐cleavage of the interglycosidic (O‐C2′) bond, hence diastereomers at C‐2′ are also obtained in 12% yield. The 4‐O‐allyl‐protected sucrose‐5‐ene 3 is similarly transformed into the corresponding (1 → 2′) ether‐linked pseudo‐disaccharide 4, illustrating the compatibility of the allyl group with the TIBAL reaction conditions.magnified image