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Theoretical study on the ring-opening reactions of cyclopropenes mediated by a AuI complex
Citation
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
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.
Item Details
Item Type: | Refereed Article |
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Keywords: | cyclopropenes |
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 |
Downloads: | 0 |
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