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A molecular electron density theory study of the [3 + 2] cycloaddition reaction of nitrones with ketenes

AuthorsRíos-Gutiérrez, Mar; Darù, Andrea; Tejero, Tomás CSIC ORCID; Domingo, Luis R.; Merino, Pedro CSIC ORCID
Issue Date2017
PublisherRoyal Society of Chemistry (UK)
CitationOrganic and Biomolecular Chemistry 15(7): 1618-1627 (2017)
AbstractThe [3 + 2] cycloaddition (32CA) reaction between nitrones and ketenes has been studied within the Molecular Electron Density Theory (MEDT) at the Density Functional Theory (DFT) MPWB1K/6-311G(d,p) computational level. Analysis of the conceptual DFT reactivity indices allows the explanation of the reactivity, and the chemo- and regioselectivity experimentally observed. The particular mechanism of this 32CA reaction involving low electrophilic ketenes has been elucidated by using a bonding evolution theory (BET) study. It is determined that this reaction takes place in one kinetic step only but in a non-concerted manner since two stages are clearly identified. Indeed, the formation of the second C-O bond begins when the first O-C bond is already formed. This study has also been applied to predict the reactivity of nitrones with highly electrophilic ketenes. Interestingly, this study predicts a switch to a two-step mechanism due to the higher polar character of this zw-type 32CA reaction. In both cases, BET supports the non-concerted nature of the 32CA reactions between nitrones and ketenes.
Publisher version (URL)https://doi.org/10.1039/C6OB02768G
Identifiersdoi: 10.1039/C6OB02768G
issn: 1477-0520
e-issn: 1477-0539
Appears in Collections:(ISQCH) Artículos
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