Riuttamäki, S;
Laczkó, G;
Madarász, Á;
Földes, T;
Pápai, I;
Bannykh, A;
Pihko, PM;
(2022)
Carboxylate Catalyzed Isomerization of β,γ-Unsaturated N-Acetylcysteamine Thioesters**.
Chemistry - A European Journal
10.1002/chem.202201030.
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Abstract
We demonstrate herein the capacity of simple carboxylate salts – tetrametylammonium and tetramethylguanidinium pivalate – to act as catalysts in the isomerization of β,γ-unsaturated thioesters to α,β-unsaturated thioesters. The carboxylate catalysts gave reaction rates comparable to those obtained with DBU, but with fewer side reactions. The reaction exhibits a normal secondary kinetic isotope effect (k1H/k1D=1.065±0.026) with a β,γ-deuterated substrate. Computational analysis of the mechanism provides a similar value (k1H/k1D=1.05) with a mechanism where γ-reprotonation of the enolate intermediate is rate determining.
| Type: | Article |
|---|---|
| Title: | Carboxylate Catalyzed Isomerization of β,γ-Unsaturated N-Acetylcysteamine Thioesters** |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1002/chem.202201030 |
| Publisher version: | https://doi.org/10.1002/chem.202201030 |
| Language: | English |
| Additional information: | © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. |
| Keywords: | base catalysis, carboxylates, enolates, isomerization, kinetic isotope effects, reaction mechanism, thioesters |
| UCL classification: | UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy UCL > Provost and Vice Provost Offices > UCL BEAMS UCL |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10151342 |
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