Si-Linked Glycomimetics\nthrough a Stereoselective\nSilicon Transfer and Anion Addition

We report a synthesis of silicon-linked glycomimetics,\ndemonstrating\nunique structural properties and metabolic stability due to the inertness\nof the C–Si bond. Our method focuses on the stereoselective\ntransfer of silicon and anion addition, revealing that chirality at\nthe silicon atom can be controlled through kinetic resolution. This\napproach allows for the selective generation of 1,2-<i>cis</i> and 1,2-<i>trans</i> isomers via the manipulation of C2-protected\nsilicon ethers and nucleophilic opening of glycal epoxides. We achieved\nhigh selectivity at the anomeric carbon and expanded the scope to\ninclude various saccharides and substituted silanes. Our findings\nindicate that silicon transfer occurs intramolecularly and is influenced\nby the nature of the counterion and reaction conditions. Additionally,\nchiral silanes produced through our method hold promise for medicinal\nchemistry applications, addressing significant gaps in the synthesis\nand utility of glycomimetics. This work opens new avenues for the\ndevelopment of bioactive silicon-based molecules.