2,3-Carbamate mannosamine glycosyl donors in glycosylation reactions of diacetone-d-glucose. An experimental and theoretical study.

ABSTRACT

The role of the cyclic 2,3-N,O-carbamate protecting group in directing the selectivity of mannosylation reactions of diacetone-d-glucose, promoted by BSP/Tf2O via α-triflate intermediates, has been investigated through a combined computational and experimental approach. DFT calculations were used to locate the transition states leading to the α or ß anomers. These data indicate the preferential formation of the ß-adduct with mannosyl donors either equipped with the 4,6-O-benzylidene protection or without it. The synthetic results confirmed this preference, showing in both cases an α/ß selectivity of 46. This highlights a role for the 2,3-N,O-carbamate in sharp contrast with what described in the case of 2,3-O-carbonate mannosyl donors.