2024-03-29T01:56:12Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1557852020-12-10T16:24:28Zcom_10261_52707com_10261_5col_10261_52708
http://hdl.handle.net/10261/155785
10.1039/C6OB02768G
335221
A molecular electron density theory study of the [3 + 2] cycloaddition reaction of nitrones with ketenes
Royal Society of Chemistry (UK)
2017
artículo
Ríos-Gutiérrez, Mar
Darù, Andrea
Tejero, Tomás
Domingo, Luis R.
Merino, Pedro
rp00481
2017
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.
Gobierno de Aragón
European Commission
Ministerio de Economía y Competitividad (España)
Organic and Biomolecular Chemistry
2017
15
1618
1627