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Computational study and kinetic analysis of the aminolysis of thiolactones

Gilles Desmet (UGent) , Dagmar D'hooge (UGent) , Maarten Sabbe (UGent) , Guy Marin (UGent) , Filip Du Prez (UGent) , Pieter Espeel (UGent) and Marie-Françoise Reyniers (UGent)
(2015) JOURNAL OF ORGANIC CHEMISTRY. 80(17). p.8520-8529
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Abstract
The aminolysis of three differently alpha-substituted gamma-thiolactones (C4H5OSX, X = H, NH2, and NH(CO)-CH3) is modeled based on CBS-QB3 calculated free energies corrected for solvation using COSMO-RS. For the first time, quantitative kinetic and thermodynamic data are provided for the concerted path and the stepwise path over a neutral tetrahedral intermediate. These paths can take place via an unassisted, an amine-assisted, or a thiol-assisted mechanism. Amine assistance lowers the free energy barriers along both paths, while thiol assistance only lowers the formation of the neutral tetrahedral intermediate. Based on the ab initio calculated rate coefficients, a kinetic model is constructed that is able to reliably describe experimental observations for the aminolysis of N-acetyl-DL-homocysteine thiolactone with n-butylamine in THF and CHCl3. Reaction path analysis shows that for all conditions relevant for applications in polymer synthesis and postpolymer modification, an assisted stepwise mechanism is operative in which the formation of the neutral tetrahedral intermediate is rate-determining and which is mainly amine-assisted at low conversions and thiol-assisted at high conversions.
Keywords
ONE-POT, THIOL-ENE, HOMOCYSTEINE THIOLACTONE, MECHANISM, ENE CLICK CHEMISTRY, POLYMERS, TOOL, POLYMERIZATION, POWERFUL, ESTERS

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Chicago
Desmet, Gilles, Dagmar D’hooge, Maarten Sabbe, Guy Marin, Filip Du Prez, Pieter Espeel, and Marie-Françoise Reyniers. 2015. “Computational Study and Kinetic Analysis of the Aminolysis of Thiolactones.” Journal of Organic Chemistry 80 (17): 8520–8529.
APA
Desmet, Gilles, D’hooge, D., Sabbe, M., Marin, G., Du Prez, F., Espeel, P., & Reyniers, M.-F. (2015). Computational study and kinetic analysis of the aminolysis of thiolactones. JOURNAL OF ORGANIC CHEMISTRY, 80(17), 8520–8529.
Vancouver
1.
Desmet G, D’hooge D, Sabbe M, Marin G, Du Prez F, Espeel P, et al. Computational study and kinetic analysis of the aminolysis of thiolactones. JOURNAL OF ORGANIC CHEMISTRY. 2015;80(17):8520–9.
MLA
Desmet, Gilles, Dagmar D’hooge, Maarten Sabbe, et al. “Computational Study and Kinetic Analysis of the Aminolysis of Thiolactones.” JOURNAL OF ORGANIC CHEMISTRY 80.17 (2015): 8520–8529. Print.
@article{6970692,
  abstract     = {The aminolysis of three differently alpha-substituted gamma-thiolactones (C4H5OSX, X = H, NH2, and NH(CO)-CH3) is modeled based on CBS-QB3 calculated free energies corrected for solvation using COSMO-RS. For the first time, quantitative kinetic and thermodynamic data are provided for the concerted path and the stepwise path over a neutral tetrahedral intermediate. These paths can take place via an unassisted, an amine-assisted, or a thiol-assisted mechanism. Amine assistance lowers the free energy barriers along both paths, while thiol assistance only lowers the formation of the neutral tetrahedral intermediate. Based on the ab initio calculated rate coefficients, a kinetic model is constructed that is able to reliably describe experimental observations for the aminolysis of N-acetyl-DL-homocysteine thiolactone with n-butylamine in THF and CHCl3. Reaction path analysis shows that for all conditions relevant for applications in polymer synthesis and postpolymer modification, an assisted stepwise mechanism is operative in which the formation of the neutral tetrahedral intermediate is rate-determining and which is mainly amine-assisted at low conversions and thiol-assisted at high conversions.},
  author       = {Desmet, Gilles and D'hooge, Dagmar and Sabbe, Maarten and Marin, Guy and Du Prez, Filip and Espeel, Pieter and Reyniers, Marie-Fran\c{c}oise},
  issn         = {0022-3263},
  journal      = {JOURNAL OF ORGANIC CHEMISTRY},
  keyword      = {ONE-POT,THIOL-ENE,HOMOCYSTEINE THIOLACTONE,MECHANISM,ENE CLICK CHEMISTRY,POLYMERS,TOOL,POLYMERIZATION,POWERFUL,ESTERS},
  language     = {eng},
  number       = {17},
  pages        = {8520--8529},
  title        = {Computational study and kinetic analysis of the aminolysis of thiolactones},
  url          = {http://dx.doi.org/10.1021/acs.joc.5b01446},
  volume       = {80},
  year         = {2015},
}

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