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 β anomers. These data indicate the preferential formation of the β−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/β selectivity of 4:6. 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.

2,3-Carbamate mannosamine glycosyl donors in glycosylation reactions of diacetone-D-glucose. An experimental and theoretical study / L. Morelli, L. Legnani, S. Ronchi, L. Confalonieri, D. Imperio, L. Toma, F. Compostella. - In: CARBOHYDRATE RESEARCH. - ISSN 0008-6215. - 509:(2021 Nov), pp. 108421.1-108421.9. [10.1016/j.carres.2021.108421]

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

L. Morelli
Primo
;
S. Ronchi;F. Compostella
Ultimo
2021

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 β anomers. These data indicate the preferential formation of the β−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/β selectivity of 4:6. 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.
1,2-Cis glycosides; carbohydrates; DFT calculations; glycosylation; β-mannosides
Settore BIO/10 - Biochimica
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/868035
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