Domingo Asensi, LR.; Pérez, P.; Aurell Piquer, MJ.; Sáez Cases, JA. (2012). Understanding the Bond Formation in Hetero Diels-Alder Reactions. An ELF Analysis of the Reaction of Nitroethylene with Dimethylvinylamine. Current Organic Chemistry. 16:2343-2351. https://doi.org/10.2174/138527212803520263
Por favor, use este identificador para citar o enlazar este ítem: http://hdl.handle.net/10251/37062
Title:
|
Understanding the Bond Formation in Hetero Diels-Alder Reactions. An ELF Analysis of the Reaction of Nitroethylene with Dimethylvinylamine
|
Author:
|
Domingo Asensi, Luis Ramon
Pérez, Patricia
Aurell Piquer, Maria José
Sáez Cases, José Antonio
|
UPV Unit:
|
Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química
|
Issued date:
|
|
Abstract:
|
[EN] The bonding evolution in hetero-Diels-Alder (HDA) reactions has been studied by an ELF analysis of the electron reorganization along the HDA reaction between nitroethylene 6 and dimethylvinylamine (DMVA) 9 at the ...[+]
[EN] The bonding evolution in hetero-Diels-Alder (HDA) reactions has been studied by an ELF analysis of the electron reorganization along the HDA reaction between nitroethylene 6 and dimethylvinylamine (DMVA) 9 at the B3LYP/6-31G* level. This cycloaddition takes place along a two-stages one-step mechanism. In the first stage of the reaction, the C1-C6 bond is formed by coupling of two pseudoradical centers positioned at the most electrophilic carbon of nitroethylene 6 and the most nucleophilic center of DMVA 9. In the second stage, the formation of the second O4-C7 bond takes place between a pseudoradical center positioned at the C7 carbon of DMVA and some electron-density provided by the lone pairs of the O4 oxygen. This behavior is in complete agreement with the analyses of the local electrophilicity and nucleophilicity indices, and the spin density of the radical anion of nitroethylene 6 and of the radical cation of DMVA 9. Finally, a relationship between the polar character of the reaction and the egioselectivity is established.
[-]
|
Subjects:
|
ELF analysis of electron reorganization
,
Formation of pseudodiradical species
,
Hetero diels-alder
|
Copyrigths:
|
Reserva de todos los derechos
|
Source:
|
Current Organic Chemistry. (issn:
1385-2728
)
|
DOI:
|
10.2174/138527212803520263
|
Publisher:
|
Bentham Science Publishers
|
Publisher version:
|
http://dx.doi.org/10.2174/138527212803520263
|
Project ID:
|
info:eu-repo/grantAgreement/FONDECYT//1100278/
info:eu-repo/grantAgreement/MICINN//CTQ2009-11027/ES/Estudios de reactividad en química orgánica/
|
Thanks:
|
We are grateful to the Spanish Government (project CTQ2009-11027/BQU), and the Fondecyt project No. 1100278. Profesor Domingo also thanks Fondecyt by support through the Cooperación Internacional
|
Type:
|
Artículo
|