Abstract: Demethylepipodophyllotoxin-.beta.-glucosides are prepared by allowing demethylepipodophyllotoxin to react with a 2,3-di-O-ester of a 1-O-trialkylsilyl-4,6-O-alkylidene-.beta.-D-glucose derivative in the presence of a Lewis acid. The 4,6-O-alkylidene group can be alkylidene, arylalkylidene, or heteroarylalkylidene and the 2,3-ester can be lower alkanoyl or haloacetyl. In a typical embodiment, demethylepipodophyllotoxin is allowed to react with 4,6-O-ethylidene-2,3-di-O-acetyl-1-O-trimethylsilyl-.beta.-D-glucose in the presence of boron trifluoride etherate to yield etoposide 2",3"-diacetate.