Abstract: One aspect of this invention relates to 2-substituted podophyllotoxin corresponding to the formula: ##STR1## where R.sub.1 is the residue of an electrophile reactant with the precursor enolate, e.g., halogen, i.e., Br, Cl, F and I, lower alkyl (preferably methyl), hydroxyl, --SR.sub.5 where R.sub.5 is lower alkyl, aralkyl or aryl and COOR.sub.6 where R.sub.6 is hydrogen or lower alkyl. Another aspect of this invention relates to 2-substituted etopsides and related compounds corresponding to the formula: ##STR2## where R.sub.1 is as defined above, and where R.sub.2 is: ##STR3## where AcO is acetyl; or ##STR4## where R.sub.3 is hydrogen and R.sub.4 is alkyl, alkenyl, cycloalkyl, 2-furyl, 2-thienyl, aryl, aralkyl, or alkenyl wherein the aromatic ring (preferably phenyl) may be optionally substituted by one or more hydroxyl, alkyl, alkoxy, nitro or halogen; or where each of R.sub.3 and R.sub.4 is alkyl or where each of R.sub.3 and R.sub.