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Revisiting the mechanism of acetylenic amine N-Oxide rearrangement catalysed by Gold(I) complexes from a DFT perspective

Citation

Lahiji, FK and Ariafard, A, Revisiting the mechanism of acetylenic amine N-Oxide rearrangement catalysed by Gold(I) complexes from a DFT perspective, Journal of Organometallic Chemistry, 889 pp. 45-52. ISSN 0022-328X (2019) [Refereed Article]

Copyright Statement

2019 Elsevier B.V. All rights reserved.

DOI: doi:10.1016/j.jorganchem.2019.03.011

Abstract

In this study, we used density functional theory (DFT) to reinvestigate the mechanism proposed by Houk and Zhang et al. (J. Am. Chem. Soc. 2012, 134, 1078) for piperidinone formation through rearrangement of an acetylenic amine N-oxide catalysed by phosphine gold(I) complexes. For this rearrangement, the C-C coupling was proposed to be the rate-determining step with activation energy as high as 35.8 kcal/mol. Such a barrier seems inconsistent with the fact that the actual reaction proceeds under very mild conditions (0 C, 1 h, in CH2Cl2). In the original report, it was proposed that the C-C coupling takes place via a mechanism which we called "front-side addition". Interestingly, we found that the C-C coupling step becomes energetically more favourable if it occurs via another mechanism called "back-side addition". We explored the effect of different phosphine ligands on all conceivable steps of the catalytic reaction and found that while the other steps are not highly sensitive to the phosphine identity, the C-C coupling one shows a considerable degree of dependency; the more electron-donating the phosphine ligand, the lower the rate-limiting step barrier.

Item Details

Item Type:Refereed Article
Keywords:density functional theory, activation energy, aamine N-oxide, alkyne, mechanistic study
Research Division:Chemical Sciences
Research Group:Organic Chemistry
Research Field:Physical Organic 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:134451
Year Published:2019
Funding Support:Australian Research Council (DP180100904)
Deposited By:Chemistry
Deposited On:2019-08-13
Last Modified:2019-12-10
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