Non-classical C-saccharide linkage of dehydroalanine: synthesis of C-glycoamino acids and C-glycopeptides

Herein, a non-classical C-saccharide linkage is reported via a C5 radical of pentose or C6 radical of hexose addition to Michael acceptors. C(sp3)-S cleaved glycosyl thianthrenium salts are developed as the glycosyl radical agents. The reaction provides an efficient toolkit to synthesize β-glycosyl substituted unnatural amino acids as well as for the late-stage C-saccharide modification of peptides.