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Issue 5, 2019
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Insights into highly selective ring expansion of oxaziridines under Lewis base catalysis: a DFT study

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Abstract

The competing mechanisms of the highly selective ring expansion reaction of oxaziridines catalyzed by N-heterocyclic carbenes (NHCs) have been theoretically studied by density functional theory (DFT). The calculated results indicate that the overall catalytic cycle includes two stages, i.e., the formation of an enolate intermediate and the ring expansion of oxaziridines. The C–O bond formation step in stage 2 was found to be both the stereoselectivity-determining and rate-determining step. The non-covalent interaction (NCI) analysis indicates that the R-configurational pathway has more hydrogen bonds so that the corresponding product is energetically favorable. The global reactivity index (GRI) analysis reveals that the enolate intermediate is the nucleophilic reagent. Furthermore, the calculated results indicate that the efficiency of different Lewis base organocatalysts would be predicted by calculating the nucleophilicity index N values of the corresponding enolate intermediates.

Graphical abstract: Insights into highly selective ring expansion of oxaziridines under Lewis base catalysis: a DFT study

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Publication details

The article was received on 18 Dec 2018, accepted on 24 Jan 2019 and first published on 25 Jan 2019


Article type: Research Article
DOI: 10.1039/C8QO01370E
Org. Chem. Front., 2019,6, 679-687

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    Insights into highly selective ring expansion of oxaziridines under Lewis base catalysis: a DFT study

    Q. Zhang, X. Li, X. Wang, S. Li, L. Qu, Y. Lan and D. Wei, Org. Chem. Front., 2019, 6, 679
    DOI: 10.1039/C8QO01370E

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