Visible‐Light‐Induced Stereoselective C(sp3)−C(sp3)−H Glycosylation for the Synthesis of C‐Glycoamino Acid Derivatives

Abstract Chiral C‐Glycosyl amino acids are prevalent structural motifs found in pharmaceuticals and natural products, making them a significant dimension for exploration in modern pharmaceutical and medicinal chemistry. However, the current synthesis methods for these compounds face numerous environmental and practical challenges, highlighting the critical need to establish more sustainable approaches. Herein, we report a simple and powerful strategy for the stereoselective synthesis of C‐glycoamino acids derivatives. This method features the design and use of (−)/(+)‐camphorsultam as an ideal chiral auxiliary, shielding one prochiral face of the glycine α‐carbon efficiently and imposing a high kinetic barrier for the epimerization of thus‐generated chiral α‐carbon that two configuration products of R and S could be achieved independently. It proceeds under mild conditions, shows broad scope, and allows for the direct stereoselective glycosylation without metal and chiral ligand.