Nonenzymatic Stereoselective <i>S</i> -Glycosylation of Polypeptides and Proteins
Liqiang Wan, Xia Zhang, Yike Zou, Rong Shi, Jin-Ge Cao, Shiyang Xu, Li‐Fan Deng, Li Zhou, Yanqiu Gong, Xiaoling Shu, Ga Young Lee, Haiyan Ren, Lunzhi Dai, Shiqian Qi, K. N. Houk, Dawen Niu
Abstract
-glycosidic bonds under biorelevant conditions. This strategy is enabled by the design and use of allyl glycosyl sulfones as precursors to glycosyl radicals and exploits the exceptional functional group tolerance of radical processes. Our method introduces a variety of unprotected glycosyl units to the cysteine residues of peptides in a highly selective fashion. Through developing the second-generation protocol, we applied our method in the direct glycosylation of complex polypeptides and proteins. Computational studies were performed to elucidate the reaction mechanism.