Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Stereoselectivity of Conformationally Restricted Glucosazide Donors

Stereoselectivity of Conformationally Restricted Glucosazide Donors
Stefan van der Vorm, Gijsbert A. van der Marel, Jeroen D. C. Codée, Herman S. Overkleeft
Glycosylations of 4,6-tethered glucosazide donors with a panel of model acceptors revealed the effect of acceptor nucleophilicity on the stereoselectivity of these donors. The differences in reactivity among the donors were evaluated in competitive glycosylation reactions, and their relative reactivities were found to be reflected in the stereoselectivity in glycosylations with a set of fluorinated alcohols as well as carbohydrate acceptors. We found that the 2-azido-2-deoxy moiety is more β-directing than its C-2-O-benzyl counterpart, as a consequence of increased destabilization of anomeric charge development by the electron-withdrawing azide. Additional disarming groups further decreased the α-selectivity of the studied donors, whereas substitution of the 4,6-benzylidene acetal with a 4,6-di-tert-butyl silylidene led to a slight increase in α-selectivity. The C-2-dinitropyridone group was also explored as an alternative for the nonparticipating azide group, but this protecting group significantly increased β-selectivity. All studied donors exhibited the same acceptor-dependent selectivity trend, and good α-selectivity could be obtained with the weakest acceptors and most reactive donors.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00470

DOI: 10.1021/acs.joc.7b00470

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