2024-03-28T14:16:19Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1868682020-05-11T09:02:14Zcom_10261_52707com_10261_5col_10261_52708
DIGITAL.CSIC
author
Chiacchio, Maria A.
author
Legnani, Laura
author
Caramella, Pierluigi
author
Tejero, Tomás
author
Merino, Pedro
funder
Ministerio de Economía y Competitividad (España)
funder
European Commission
funder
Gobierno de Aragón
funder
Università degli Studi di Catania
funder
Università degli studi di Pavia
2019-07-25T11:06:57Z
2019-07-25T11:06:57Z
2018
Tetrahedron 74(39): 5627-5634 (2018)
0040-4020
http://hdl.handle.net/10261/186868
10.1016/j.tet.2018.07.056
http://dx.doi.org/10.13039/501100010067http://dx.doi.org/10.13039/501100004769http://dx.doi.org/10.13039/501100003329http://dx.doi.org/10.13039/501100000780
The ene-type reaction between (dithio)carboxylic acids and alkenes has been studied computationally by DFT and topological (analysis of the electron localization function, ELF) methods. The reaction proceeds under kinetic control and the observed differences in regioselectivity are well-explained by the relative stability of the different transition structures. In agreement with experimental observations, electron-rich alkenes lead to Markownikoff adducts while electron-poor alkenes lead to Michael adducts. In all cases the reaction proceeds through an only transition structure (one kinetic step) although a different synchronicity was observed depending on the alkene electronics. The ELF analysis of the reactions corroborates the existence of a transient carbocation (hidden intermediate) in the reactions with electron-rich alkenes. On the other hand, electron-poor alkenes proceed through a more synchronous concerted mechanism. It can be predicted that with electron-rich alkenes bearing highly donating the transient carbocations might be captured by a nucleophile.
eng
closedAccess
Ene-reaction
Hidden intermediates
Dithiocarboxylic acids
Carbocations
ELF analysis
Revealing carbocations in highly asynchronous concerted reactions: The ene-type reaction between dithiocarboxylic acids and alkenes
artículo
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URL
https://digital.csic.es/bitstream/10261/186868/1/accesoRestringido.pdf
File
MD5
b83c8ac165767da5ebe109ca46dab524
60665
application/pdf
accesoRestringido.pdf