biostudies-literatureUnknown631(8020)Jiang YNaturally occurring (native) sugars and carbohydrates contain numerous hydroxyl groups of similar reactivity^1,2. Chemists, therefore, rely typically on laborious, multi-step protecting-group strategies³ to convert these renewable feedstocks into reagents (glycosyl donors) to make glycans. The direct transformation of native sugars to complex saccharides remains a notable challenge. Here we describe a photoinduced approach to achieve site- and stereoselective chemical glycosylation from widely available native sugar building blocks, which through homolytic (one-electron) chemistry bypasses unnecessary hydroxyl group masking and manipulation. This process is reminiscent of nature in its regiocontrolled generation of a transient glycosyl donor, followed by radical-based Nature319-327https://www.ebi.ac.uk/biostudies/studies/S-EPMC11236704biostudies-literatureDirect radical functionalization of native sugars.PMC11236704Jiang YSong NLevin NMohammed SZhang YDavis BGFu XPSun GQWei YZhou QYKoh MJLiu WQfalseDirect radical functionalization of native sugars.Naturally occurring (native) sugars and carbohydrates contain numerous hydroxyl groups of similar reactivity^1,2. Chemists, therefore, rely typically on laborious, multi-step protecting-group strategies³ to convert these renewable feedstocks into reagents (glycosyl donors) to make glycans. The direct transformation of native sugars to complex saccharides remains a notable challenge. Here we describe a photoinduced approach to achieve site- and stereoselective chemical glycosylation from widely available native sugar building blocks, which through homolytic (one-electron) chemistry bypasses unnecessary hydroxyl group masking and manipulation. This process is reminiscent of nature in its regiocontrolled generation of a transient glycosyl donor, followed by radical-based 2024-01-01T00:00:00Z2024 Jul2025-04-05T15:49:02.648Z2025-04-05T15:49:02.648ZS-EPMC112367043889827510.1038/s41586-024-07548-0