2-Nitro-thioglycosides: α- and β-selective generation and their potential as β-selective glycosyl donors
Peng Peng1, Yiqun Geng1, Inigo Göttker-Schnetmann1
1Department of Chemistry, University of Konstanz, 78457 Konstanz, Germany.
Abstract:
Michael-type addition of thiolates to 2-nitro-D-glucal or to 2-nitro-D-galactal derivatives readily provides 2-deoxy-2-nitro-1-thioglycosides. Kinetic and thermodynamic reaction control permitted formation of either the α- or preferentially the β-anomers, respectively. Addition of achiral and chiral thiourea derivatives to the reaction mixture increased the reaction rate; the outcome is substrate-controlled. The 2-deoxy-2-nitro-1-thioglycosides are excellent glycosyl donors under arylsulfenyl chloride/silver triflate (ArSCl/AgOTf) activation, and they provide, anchimerically assisted by the nitro group, mostly β-glycosides.
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