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Quantitative first-principles kinetic modeling of the aza-Michael addition to acrylates in polar aprotic solvents

(2016) JOURNAL OF ORGANIC CHEMISTRY. 81(24). p.12291-12302
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Abstract
This work presents a detailed computational study and kinetic analysis of the aza-Michael addition of primary and secondary amines to acrylates in an aprotic solvent. Accurate rate coefficients for all elementary steps in the various competing mechanisms are calculated using an ONIOM-based approach in which the full system is calculated with M06-2X/6-311+G(d,p) and the core system with CBS-QB3 corrected for solvation using COSMO-RS. Diffusional contributions are taken into account using the coupled encounter pair model with diffusion coefficients calculated based on molecular dynamics simulations. The calculated thermodynamic and kinetic parameters for all forward and reverse elementary reactions are fed to a microkinetic model giving excellent agreement with experimental data obtained using GC analysis. Rate analysis reveals that for primary and secondary amines, the aza-Michael addition to ethyl acrylate occurs preferentially according to a 1,2-addition mechanism, consisting of the pseudoequilibrated formation of a zwitterion followed by a rate controlling amine assisted proton transfer toward the singly substituted product. The alternative 1,4-addition becomes competitive if substituents are present on the amine or double bond of the acrylate. Primary amines react faster than secondary amines due to increased solvation of the zwitterionic intermediate and less sterically hindered proton transfer.
Keywords
ALPHA, BETA-UNSATURATED KETONES, NUCLEOPHILIC-ADDITION, MOLECULAR-MECHANICS, CATALYST-FREE, ONE-POT, AMINES, POLYMERIZATION, AMINOLYSIS, CHEMISTRY, TOOL

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Chicago
Desmet, Gilles, Dagmar D’hooge, Pinar Sinem Omurtag, Pieter Espeel, Guy Marin, Filip Du Prez, and Marie-Françoise Reyniers. 2016. “Quantitative First-principles Kinetic Modeling of the aza-Michael Addition to Acrylates in Polar Aprotic Solvents.” Journal of Organic Chemistry 81 (24): 12291–12302.
APA
Desmet, Gilles, D’hooge, D., Omurtag, P. S., Espeel, P., Marin, G., Du Prez, F., & Reyniers, M.-F. (2016). Quantitative first-principles kinetic modeling of the aza-Michael addition to acrylates in polar aprotic solvents. JOURNAL OF ORGANIC CHEMISTRY, 81(24), 12291–12302.
Vancouver
1.
Desmet G, D’hooge D, Omurtag PS, Espeel P, Marin G, Du Prez F, et al. Quantitative first-principles kinetic modeling of the aza-Michael addition to acrylates in polar aprotic solvents. JOURNAL OF ORGANIC CHEMISTRY. 2016;81(24):12291–302.
MLA
Desmet, Gilles, Dagmar D’hooge, Pinar Sinem Omurtag, et al. “Quantitative First-principles Kinetic Modeling of the aza-Michael Addition to Acrylates in Polar Aprotic Solvents.” JOURNAL OF ORGANIC CHEMISTRY 81.24 (2016): 12291–12302. Print.
@article{8507449,
  abstract     = {This work presents a detailed computational study and kinetic analysis of the aza-Michael addition of primary and secondary amines to acrylates in an aprotic solvent. Accurate rate coefficients for all elementary steps in the various competing mechanisms are calculated using an ONIOM-based approach in which the full system is calculated with M06-2X/6-311+G(d,p) and the core system with CBS-QB3 corrected for solvation using COSMO-RS. Diffusional contributions are taken into account using the coupled encounter pair model with diffusion coefficients calculated based on molecular dynamics simulations. The calculated thermodynamic and kinetic parameters for all forward and reverse elementary reactions are fed to a microkinetic model giving excellent agreement with experimental data obtained using GC analysis. Rate analysis reveals that for primary and secondary amines, the aza-Michael addition to ethyl acrylate occurs preferentially according to a 1,2-addition mechanism, consisting of the pseudoequilibrated formation of a zwitterion followed by a rate controlling amine assisted proton transfer toward the singly substituted product. The alternative 1,4-addition becomes competitive if substituents are present on the amine or double bond of the acrylate. Primary amines react faster than secondary amines due to increased solvation of the zwitterionic intermediate and less sterically hindered proton transfer.},
  author       = {Desmet, Gilles and D'hooge, Dagmar and Omurtag, Pinar Sinem and Espeel, Pieter and Marin, Guy and Du Prez, Filip and Reyniers, Marie-Fran\c{c}oise},
  issn         = {0022-3263},
  journal      = {JOURNAL OF ORGANIC CHEMISTRY},
  language     = {eng},
  number       = {24},
  pages        = {12291--12302},
  title        = {Quantitative first-principles kinetic modeling of the aza-Michael addition to acrylates in polar aprotic solvents},
  url          = {http://dx.doi.org/10.1021/acs.joc.6b02218},
  volume       = {81},
  year         = {2016},
}

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