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

Lahiji, FK and Ariafard, A ORCID: 0000-0003-2383-6380 2019 , 'Revisiting the mechanism of acetylenic amine N-Oxide rearrangement catalysed by Gold(I) complexes from a DFT perspective' , Journal of Organometallic Chemistry, vol. 889 , pp. 45-52 , doi: 10.1016/j.jorganchem.2019.03.011.

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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 Type: Article
Authors/Creators:Lahiji, FK and Ariafard, A
Keywords: density functional theory, activation energy, aamine N-oxide, alkyne, mechanistic study
Journal or Publication Title: Journal of Organometallic Chemistry
Publisher: Elsevier
ISSN: 0022-328X
DOI / ID Number: 10.1016/j.jorganchem.2019.03.011
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© 2019 Elsevier B.V. All rights reserved.

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