Sigmatropic shifts and cycloadditions on neutral, cationic, and anionic pentadienyl+butadiene potential energy surfaces

Quantum chemical calculations were used to characterize [4,5] sigmatropic shifts in systems containing butadiene and pentadienyl substructures. Cationic, anionic, and radical systems with various tethers connecting these substructures were examined. In many cases, concerted [4,5] sigmatropic shifts with asynchronous bond making and breaking events were observed. The fundamental connections between [4,5] sigmatropic shifts and (5+4) cycloadditions are highlighted.