Ph3PO-Modulated Kdo Glycosidation for Stereoselective Synthesis of β-Kdo-Containing Disaccharides

A Ph3PO-modulated β-selective Kdo glycosidation approach is developed for the stereoselective synthesis of β-Kdo glycosides. With the readily available per-O-acetylated Kdo ynenoate as the donor, the glycosylation with a series of alcohols in the presence of Ph3PAuOTf and Ph3PO in toluene at low temperatures afforded the desired Kdo glycosides with good to excellent β-selectivities. Furthermore, the Ph3PO-modulated approach was effectively applied to the synthesis of β-(2→4)- and β-(2→8)-linked Kdo-Kdo disaccharides for further biological studies.