Stereochemical Differentiation in the Simmons-Smith Reaction for Cyclopropanated Glucopyranose Derivatives as Molecular Probes for Glycosidases

Glucopyranose analogues carrying a bicyclo[4.1.0]heptane framework (4) and the diastereomer of the cyclopropane moiety were synthesized as the unit for molecular probes to mimic the unstable transition state conformation of the glucopyranose ring in enzymatic hydrolysis. The synthesis features differentiation of the α- and β-stereoselectivity in cyclopropanation of the corresponding cyclohexene derivative (5).