title: Theoretical study on the ring-opening reactions of cyclopropenes mediated by a AuI complex.
abstract: 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 ΔE(++) 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.
authors: Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University , Shahrak Gharb, Tehran, Iran.
authors: Nasir Ahmad
authors: NA
authors: Rajabi
authors: Mona Jalali
authors: MJ
authors: Atashgah
authors: Rasool
authors: R
authors: BabaAhmadi
authors: Christopher
authors: C
authors: Hyland
authors: Alireza
authors: A
authors: Ariafard