Synthesis of 5‐glycosylated β‐anhydroicaritine

Abstract Glycosylation plays an important role in many biological processes, and its structural changes have a significant impact on biological activity. Unlike natural icariin, icariside I, and icariside II, a simulated unnatural 5‐glycosylation ( 4 ) was designed to expand substrate adaptability and the pharmacological properties of the parent compound. Therefore, starting from commercially available icaritin, 5‐glycosylated icaritin was successfully synthesized in moderate yield through cyclization, selective 3‐alkylation, 5‐glycosylation, and hydrogenation steps. The structure was identified by 1 H nuclear magnetic resonance (NMR), 13 C NMR, MS, and x‐ray spectroscopy.