A1 Journal article (refereed)
Carboxylate catalyzed isomerization of β,γ‐unsaturated N-acetylcysteamine thioesters (2022)

Riuttamäki, S., Laszkó, G., Madarász, Á., Földes, T., Pápai, I., Bannykh, A., & Pihko, P. M. (2022). Carboxylate catalyzed isomerization of β,γ‐unsaturated N-acetylcysteamine thioesters. Chemistry : A European Journal, 28(45), Article e202201030. https://doi.org/10.1002/chem.202201030

JYU authors or editors

Riuttamäki, Saara
Bannykh, Anton
Pihko, Petri

Publication details

All authors or editors: Riuttamäki, Saara; Laszkó, Gergely; Madarász, Ádam; Földes, Tamás; Pápai, Imre; Bannykh, Anton; Pihko, Petri M.

Journal or series: Chemistry : A European Journal

ISSN: 0947-6539

eISSN: 1521-3765

Publication year: 2022

Publication date: 23/05/2022

Volume: 28

Issue number: 45

Article number: e202201030

Publisher: Wiley-VCH Verlag

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/chem.202201030

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/82617

Web address of parallel published publication (pre-print): https://doi.org/10.26434/chemrxiv-2022-cvmqf

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 ( k 1H / k 1D = 1.065±0.026) with a β,γ−deuterated substrate. Computational analysis of the mechanism provides a similar value ( k 1H / k 1D = 1.05) with a mechanism where γ-reprotonation of the enolate intermediate is rate determining.

Keywords: organic compounds; sulphur compounds; isomerism; catalysis; catalysts; reaction mechanisms

Free keywords: base catalysis; isomerization; carboxylates; kinetic isotope effects; reaction mechanism; thioesters; enolates

Fields of science: