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DFT-based comparison between mechanistic aspects of amine and alcohol oxidation mediated by IBX

Chipman, A, Farshadfar, K, Smith, JA ORCID: 0000-0001-6313-3298, Yates, BF ORCID: 0000-0001-9663-3301 and Ariafard, A ORCID: 0000-0003-2383-6380 2019 , 'DFT-based comparison between mechanistic aspects of amine and alcohol oxidation mediated by IBX' , Journal of Organic Chemistry, vol. 85, no. 2 , pp. 515-525 , doi: 10.1021/acs.joc.9b02583.

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Density functional theory was utilized to investigate plausible mechanisms for amine and alcohol oxidation by an iodine(V) hypervalent reagent (IBX). In this contribution, we found that amine and alcohol oxidation both proceed by similar mechanisms. The reactions initiate from ligand exchange to give four coordinate intermediates followed by a redox process giving an iodine(III) species and oxidized substrates. Interestingly, for both the ligand-exchange and the redox steps a hypervalent twist is required for the reaction to proceed via an energetically more accessible route. The ligand-exchange process was found to be mediated by a proton-shuttling agent such as water, a second IBX, or a second substrate. While the ligand-exchange step for both amine and alcohol occurs with almost identical activation energy (particularly when water is considered as the shuttling agent), the redox step for the amine takes place with much lower activation energy than that for the alcohol. Finally, we ascertained that five coordinate amide iodine(V) complexes are unreactive toward redox reactions due to the fact that in such cases two electrons from the coordinated amide are required to occupy a 3c–4e σ* orbital which is too high in energy to be reachable.

Item Type: Article
Authors/Creators:Chipman, A and Farshadfar, K and Smith, JA and Yates, BF and Ariafard, A
Keywords: amine oxidation, alcohol oxidation, IBX, hypervalent iodine, Density Functional Theory, mechanistic investigation
Journal or Publication Title: Journal of Organic Chemistry
Publisher: Amer Chemical Soc
ISSN: 0022-3263
DOI / ID Number: 10.1021/acs.joc.9b02583
Copyright Information:

© 2019 American Chemical Society

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