Stereoselective Synthesis of Glycomimetics via Photo-HAT/Nickel Dual-Catalysis

Abstract Carbohydrates not only serve as energy sources for organisms but also perform numerous critical physiological functions. However, the inherent instability of the O-glycosidic bonds restricts their application as therapeutic agents, and glycomimetics (including C-glycosides, branched-chain sugars, and carbasugars) have emerged as highly promising carbohydrate surrogates. We have developed a photoinduced hydrogen atom transfer (Photo-HAT)/nickel dual-catalytic system, which enables direct and stereoselective C(sp3)–H bond functionalization of carbohydrates, thereby providing a novel technology for the efficient synthesis of diverse rare sugars such as C-glycosides, branched-chain sugars, and carbasugars.