Journal
ORGANIC & BIOMOLECULAR CHEMISTRY
Volume 15, Issue 7, Pages 1618-1627Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6ob02768g
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Funding
- Spanish MINECO [FEDER CTQ2016-78669-P, CTQ2016-76155-R]
- Government of Aragon (Grupos Consolidados) [E.10]
- MINECO - European Social Fund [BES-2014-068258]
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The [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.
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