Regiodivergent Functionalization of Protected and Unprotected Carbohydrates using Photoactive 4‐Tetrafluoropyridinylthio Fragment as an Adaptive Activating Group

The selective functionalization of carbohydrates holds a central position in synthetic carbohydrate chemistry, driving the ongoing quest for ideal approaches to manipulate these compounds. In this study, we introduce a general strategy that enables the regiodivergent functionalization of saccharides. The use of electron‐deficient photoactive 4‐tetrafluoropyridinylthio (SPyf) fragment as an adaptable activating group, facilitated efficient functionalization across all saccharide sites. More importantly, this activating group can be directly installed at the C1, C5 and C6 positions of biomass‐derived carbohydrates in a single step and in a site‐selective manner, allowing for the efficient and precision‐oriented modification of unprotected saccharides and glycans. A general platform has been developed for the regiodivergent functionalization of both protected and unprotected carbohydrates by utilizing the electron‐deficient thiyl fragment as a versatile and adaptive activating group. This method facilitates the efficient generation of carbon radicals at different saccharide sites, providing a valuable tool for the expeditous synthesis of a diverse array of high‐value C‐glycosides and rare sugars.