Photoredox/Cobalt‐Catalyzed Asymmetric Radical Addition to Imines with Furanosyl 1,4‐Dihydropyridines to Access <i>C</i> ‐Glycosyl Amino Esters

Chiral oxygen-containing heterocycles, particularly tetrahydrofuran scaffolds are pivotal structures found in numerous bioactive molecules. Among them, furanoses constitute a highly important class. While C-glycosylation with furanosyl donors offers a promising route to access these frameworks, methods for simultaneously constructing multiple stereogenic centers remain unknown. Herein, we report a synergistic photoredox/cobalt-catalyzed enantioselective radical addition strategy to imines that employs bench-stable furanosyl 1,4-dihydropyridines (DHPs) as the radical precursors. This redox-neutral protocol directly forges C-glycosidic bonds at the challenging non-anomeric position while concurrently establishing a new tetrasubstituted carbon stereocenter. The chiral cobalt catalyst effectively governs the stereochemistry of both the glycosidic bond and the new tetrasubstituted center, as evidenced by ligand control experiments. Furthermore, the method is generalizable to simple alkyl-substituted DHPs, providing a versatile and complementary approach to synthesize amino esters and C-glycosides with multiple stereogenic centers.