The Diels–Alder Reaction of Ethene and 1,3-Butadiene: An Extended Multireference ab initio Investigation

The concerted and stepwise mechanisms of the Diels–Alder reaction between 1,3-butadiene and ethene have been investigated using highly correlated multireference methods (MRAQCC) and extended basis sets. Full MRAQCC geometry optimizations have been performed in all cases. The best estimate for the energy barrier of the Diels–Alder reaction is 22 kcal mol⁻¹. Anti- and gauche-out minima for the biradical structures and corresponding fragmentation saddle points have been determined. The biradical anti fragmentation saddle point is located 6.5 kcal mol⁻¹ above the concerted saddle point. The gauche-in structure does not correspond to a local minimum, but leads on geometry optimization directly to cyclohexene.