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


Rajabi, NA and Atashgah, MJ and Babaahmadi, R and Hyland, C and Ariafard, A, Theoretical study on the ring-opening reactions of cyclopropenes mediated by a AuI complex, The Journal of Organic Chemistry, 78, (19) pp. 9553-9559. ISSN 0022-3263 (2013) [Refereed Article]

Copyright Statement

Copyright 2013 American Chemical Society

DOI: doi:10.1021/jo401544e


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 C1C3 bond. An excellent correlation between ΔE and the difference in the C1C2 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.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Babaahmadi, R (Mr Rasool Babaahmadi)
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:89197
Year Published:2013
Web of Science® Times Cited:19
Deposited By:Chemistry
Deposited On:2014-02-26
Last Modified:2021-05-12

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