The synthesis of 14beta-acylaminocodeinones has been achieved via the Diels-Alder addition of nitrosocarbonyl-compounds to the activated diene system of the baine. Several variations on this route have been investigated and the most efficient yields the desired products in greater than 60% yield from the baine. The analgesic properties and structure/activity relationships of several of these compounds and their precursors with differing alkyl and aryl side chains have been established.