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A facile synthesis of 2-ethynylpyrroles by ButOK-assisted room temperature deprotection of 2-(acylethynyl)pyrroles

Denis Nikolaevich Tomilin 1
Denis Nikolaevich Tomilin
,  , 
Alexander Borisovich Trofimov 1, 2
Alexander Borisovich Trofimov
, 
Alexandra Maksimovna Belogolova 1, 3
Alexandra Maksimovna Belogolova
, 
Igor Alekseevich Ushakov 1
Igor Alekseevich Ushakov
, 
Nina Savel'evna Shaglaeva 4
Nina Savel'evna Shaglaeva
, 
Boris Aleksandrovich Trofimov 1
Boris Aleksandrovich Trofimov
2 Laboratory of Quantum Chemical Modeling of Molecular Systems, Irkutsk State University, Irkutsk, Russian Federation
3 Faculty of Physics, Irkutsk State University, Irkutsk, Russian Federation
4 Institute of High Technologies, Irkutsk National Research Technical University, Irkutsk, Russian Federation
10.1016/j.mencom.2023.06.005
Published 2023-06-13
Communication , Volume 33, Issue 4, 458-460
3
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Tomilin D. N. et al. A facile synthesis of 2-ethynylpyrroles by ButOK-assisted room temperature deprotection of 2-(acylethynyl)pyrroles // Mendeleev Communications. 2023. Vol. 33. No. 4. pp. 458-460.
GOST all authors (up to 50) Copy
Tomilin D. N., Sobenina L. N., Trofimov A. B., Belogolova A. M., Ushakov I. A., Shaglaeva N. S., Trofimov B. A. A facile synthesis of 2-ethynylpyrroles by ButOK-assisted room temperature deprotection of 2-(acylethynyl)pyrroles // Mendeleev Communications. 2023. Vol. 33. No. 4. pp. 458-460.
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TY - JOUR
DO - 10.1016/j.mencom.2023.06.005
UR - https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.06.005
TI - A facile synthesis of 2-ethynylpyrroles by ButOK-assisted room temperature deprotection of 2-(acylethynyl)pyrroles
T2 - Mendeleev Communications
AU - Tomilin, Denis Nikolaevich
AU - Sobenina, Lyubov Nikolaevna
AU - Trofimov, Alexander Borisovich
AU - Belogolova, Alexandra Maksimovna
AU - Ushakov, Igor Alekseevich
AU - Shaglaeva, Nina Savel'evna
AU - Trofimov, Boris Aleksandrovich
PY - 2023
DA - 2023/06/13
PB - Mendeleev Communications
SP - 458-460
IS - 4
VL - 33
ER -
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@article{2023_Tomilin,
author = {Denis Nikolaevich Tomilin and Lyubov Nikolaevna Sobenina and Alexander Borisovich Trofimov and Alexandra Maksimovna Belogolova and Igor Alekseevich Ushakov and Nina Savel'evna Shaglaeva and Boris Aleksandrovich Trofimov},
title = {A facile synthesis of 2-ethynylpyrroles by ButOK-assisted room temperature deprotection of 2-(acylethynyl)pyrroles},
journal = {Mendeleev Communications},
year = {2023},
volume = {33},
publisher = {Mendeleev Communications},
month = {Jun},
url = {https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.06.005},
number = {4},
pages = {458--460},
doi = {10.1016/j.mencom.2023.06.005}
}
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Tomilin, Denis Nikolaevich, et al. “A facile synthesis of 2-ethynylpyrroles by ButOK-assisted room temperature deprotection of 2-(acylethynyl)pyrroles.” Mendeleev Communications, vol. 33, no. 4, Jun. 2023, pp. 458-460. https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.06.005.

Keywords

(acylethynyl)pyrroles
deacylation
deprotection
ethynylpyrroles
potassium tert-butoxide.
pyrroles
terminal alkynes
ynones

Abstract

Available N-substituted 2-(acylethynyl)pyrroles undergo room temperature deprotection in the ButOK/THF system to give 2-ethynylpyrroles in 82-92% yields. Quantum-chemical calculations (B2PLYP/6-311G**//B3LYP/6-311G**+C-PCM/THF) show that the cleavage of ethynyl-acyl bond via the proton transfer from ButOK with formation of potassium acylate and 2-methylpropene is thermo-dynamically much more preferred compared to alternative nucleophilic attack of tert-butoxide anion at the acyl carbon (ΔG = -35.1 vs. -2.7 kcal mol-1).

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