A remarkably efficient method for derivatization of complex diene-containing natural products by using stabilized iminonitroso Diels-Alder reactions is described. Turimycin H3, ergosterol, reductiomycin, isoforocidin, colchicine and thebaine were found to react with nitrosopyridines in a highly efficient regio- and stereoselective fashion. Preliminary bioactivity evaluations of turimycin cycloadducts are reported.