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

Nasir Ahmad Rajabi, Mona Jalali Atashgah, Rasool Babaahmadi, Christopher Hyland, Alireza Ariafard

Research output: Contribution to journalArticle

17 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)9553-9559
Number of pages7
JournalJournal of Organic Chemistry
Volume78
Issue number19
Early online date26 Aug 2013
DOIs
Publication statusPublished - 4 Oct 2013

ASJC Scopus subject areas

  • Organic Chemistry

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