Theoretical study on the ring-opening reactions of cyclopropenes mediated by a AuI complex

DFT calculations have been carried out in order to rationalize and predict the ring-opening regioselectivity of substituted cyclopropenes in the presence of gold(I) catalysts. It has been shown that the regioselectivity of these ring-opening processes is driven by the relative π-donor ability of the substituents on the cyclopropene double bond (C1 and C2). A stronger π-donor substituent at C2 favors Au(I)-induced polarization of the double bond toward C1, resulting in preferential breaking of the C1–C3 bond. An excellent correlation between Δ<i>E</i>^⧧ and the difference in the C1–C2 p(π) orbital population was observed for a broad range of substituents, providing a useful predictive model for gold-induced cyclopropene ring-opening. Furthermore, it was found that the stability of the resulting gold-stabilized allyl-cation intermediates do not follow the same trend as the ring-opening reaction energies. Generally, the more facile ring-opening process led to the less thermodynamically stable intermediate, which lacked stabilization of the carbocation by a π-donor in the α-position.