The thermal [3,3] rearrangement of 3,3-dicyano-1,5-enynes to gamma-allenyl alkylidenemalononitriles (the "enyne Cope rearrangement") has largely eluded synthetic value as the desired products, too, are thermally reactive and ultimately yield 6 pi electrocyclization products. Herein, we describe experimental and computational studies related to the thermal rearrangement of 1,5-enynes, structural features to halt the thermal rearrangement at the allene stage, and a reductive variant for preparing bifunctional allenyl malononitriles. We also describe various ways that the bifunctional building blocks can be manipulated and converted to cyclic and acyclic architectures.