Photocatalytic\nSynthesis of α‑Ketonyl\nGlycosyl Compounds from Glycosyl Thiols and Silyl Enol Ethers

The synthesis of C1-ketonyl glycosyl compounds featuring\nα-selectivity\nhas seldom been reported. We herein devise a glycosyl radical-based\napproach to facilely access stereoenriched ketonyl glycosyl compounds\nvia an Ir photoredox-catalyzed desulfurative addition to silyl enol\nethers, using in situ-generated tetrafluoropyridinyl thioglycosides\nfrom glycosyl 1-thiols as radical precursors. This protocol features\nreadily prepared starting materials, mild conditions, excellent functional\ngroup tolerance, satisfactory scale-up, and notable amenability to\nlate-stage modification of pharmaceutically relevant complex molecules.