| Autor: |
Coutinho ND; Laboratory of Bioactive Compounds Synthesis N.T.S., University of Brasilia (IQ-UnB), Campus Universitário Darcy Ribeiro, Brasília, DF, Brazil. nayaradcoutinho@gmail.com wender@unb.br., Machado HG, Carvalho-Silva VH, da Silva WA |
| Jazyk: |
angličtina |
| Zdroj: |
Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2021 Mar 21; Vol. 23 (11), pp. 6738-6745. Date of Electronic Publication: 2021 Mar 12. |
| DOI: |
10.1039/d0cp05659f |
| Abstrakt: |
Recent studies have found that hydroxide elimination and the C[double bond, length as m-dash]C bond formation step in base-promoted aldol condensation have a strong influence on the overall rate of the reaction, in contrast to the well-accepted first enolization or C-C bond formation step. Here, applying theoretical models to the prototypical reaction of chalcone formation, the complete free energy profile of Claisen-Schmidt condensation is assessed, revealing how a protic solvent and a slight increase in temperature can induce the second enolization as the rate-controlling step (RCS). It is also observed: i) the nonexistence of a step with a much higher energetic barrier than the others, making the concept of RCS debatable; and ii) that the overall inverse kinetic isotopic effect does not exclude second enolization as a RCS in protic continuum medium. We expect that these results can expand the understanding of the decisive role of physicochemical factors on the choose of the RCS in the aldol condensation. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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