A previously unexamined approach to dyotropic rearrangements involving only atoms from the first row is tested with four substrates. Both migrating groups contain jr orbitals, either allylic or allenic. We have prepared 3,6- dimethyl-1,7-octadiene,1,2-bis(vinyloxy)ethane, ethylene diisocyanate, and ethylene dithiocyanate to test this approach. All four substrates were pyrolyzed in a sealed tube and in a flash system. Products of ene reactions, diradical rearrangements, cycloaddition, and polymerization were observed, but the dyotropic rearrangements did not take place
