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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 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.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:89197
Year Published:2013
Web of Science® Times Cited:15
Deposited By:Chemistry
Deposited On:2014-02-26
Last Modified:2017-10-25

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