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Dissection of the effects that govern thioglucoside and thiomannoside reactivity
Mads Heuckendorff1, Lulu Teressa Poulsen, Christinne Hedberg
1Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark. hhj@chem.au.dk.
Abstract:
Neighboring group effects were investigated in gluco- and manno-configured thioglycosides under NIS/TfOH activation. Donors possessing a 2-O-benzoyl group that are capable (1,2-trans) and incapable (1,2-cis) of exerting nucleophilic push were compared with donors possessing a participatory neutral 2-O-benzyl group. By using competition experiments between sets of glycosyl donors the direct effect of neighboring group participation and the electron withdrawing effect of the 2-O-benzoyl group could be separated. The study brings insight into how the stereochemistry of the 1 and 2 position and how the nature of the aglycon (Ph or Et) have a pronounced effect on glycosyl donor reactivity.
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