Ir(I)‐Catalyzed C−H Glycosylation for Synthesis of 2‐Indolyl‐C‐Deoxyglycosides

The construction of 2‐deoxy‐C‐glycosides has gradually become a hotspot of carbohydrate chemistry in recent years. In this work, we present an efficient, regioselective, stereoselective and widely applicable strategy for the synthesis of 2‐indolyl‐C‐deoxyglycosides via Ir(I)‐catalyzed, pyridine‐group‐directed C−H functionalization. This method exhibits high tolerance for the functional groups of indoles and the protecting groups of carbohydrates. Moreover, this protocol has good stereoselectivity and mainly produces β‐configuration products. Gram‐scale synthesis and several practical transformations were conducted for further applications. Meantime, we also explored the mechanism of this method and proposed a catalytic cycle