Thermal rearrangements of 1-ethynyl-2-methylcyclopropane: a computational study

In this research, a comprehensive theoretical investigation of the thermal rearrangements of 1-ethynyl-2-methylcyclopropane is carried out employing density functional theory (DFT), with the B3LYP functional, and high-level ab initio methods, such as the complete active space self-consistent field (CASSCF), multireference second-order Møller-Plesset perturbation theory (MRMP2), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)]. In all computations Pople's polarized triple-ζ split valence basis set, 6-311G(d,p), is utilized. The potential energy surface (PES) for the relevant system is explored to provide a theoretical account of the experiments by Hopf, Ellis and Frey, Huntsman et al., and Berson. The computational results herein on the target system show that the thermal aromatization reaction does not proceed via conversion of 1,2,5-hexatriene (2) to 1,3,5-hexatriene (10a) as proposed by Hopf. Indeed, the reaction proceeds via conversion of 5 and 6 to bicyclo[3.1.0]hexene (9) as suggested by Huntsman et al.