An efficient synthesis of 4 beta-aminopodophyllotoxin from 4 beta-bromopodophyllotoxin using ammonia, and also a facile synthesis of 4 beta-amino-4'-O-demethylpodophyllotoxin from 4 beta-azidopodophyllotoxin by simultaneous azido reduction and selective demethylation at 4'-position employing chlorotrimethylsilane and sodium iodide, has been described. These are potential precursors for the various 4 beta-amino analogs of podophyllotoxin possessing DNA topoisomerase II inhibition activity.