Simple Approach to Pyrrolylimidazole Derivatives by Azirine Ring Expansion with Imidazolium Ylides

Research output

13 Citations (Scopus)

Abstract

A domino reaction of 2H-azirines with 1-alkyl-3-phenacyl-1H-imidazolium bromides in the presence of Et3N provides a facile route to 1-alkyl-3-(1H-pyrrol-3-yl)-1H-imidazol-3-ium bromides. 1-Benzyl derivatives can be reduced to 1-(1H-pyrrol-3-yl)-1H-imidazoles with HCO2NH 4 on Pd/C. The action of KOH on pyrrolylimidazolium salts leads to a new type of stable ylide, 3-(1H-imidazol-3-ium-3-yl)-pyrrol-1-ides, which can, in principle, be in tautomeric equilibrium with the corresponding N-heterocyclic carbene. Although, according to the DFT B3LYP/6-31G(d) calculations in vacuo, electron-donating substituents in the 2-aryl-group cause the tautomeric equilibrium to shift to the carbene side, the investigated compounds exist in the ylide form in solution and in the solid state, which is in agreement with the relative stabilities of the species calculated with the PCM solvent model. This journal is © the Partner Organisations 2014.
Original languageEnglish
Pages (from-to)6598-6609
JournalOrganic and Biomolecular Chemistry
Volume12
Issue number34
DOIs
Publication statusPublished - 2014

Fingerprint

Bromides
imidazoles
Azirines
carbenes
Imidazoles
Derivatives
expansion
Pulse code modulation
bromides
rings
Discrete Fourier transforms
Salts
Electrons
routes
salts
solid state
causes
shift
carbene
electrons

Cite this

@article{aa1da1d7f77f4004a9cf648cd62fd318,
title = "Simple Approach to Pyrrolylimidazole Derivatives by Azirine Ring Expansion with Imidazolium Ylides",
abstract = "A domino reaction of 2H-azirines with 1-alkyl-3-phenacyl-1H-imidazolium bromides in the presence of Et3N provides a facile route to 1-alkyl-3-(1H-pyrrol-3-yl)-1H-imidazol-3-ium bromides. 1-Benzyl derivatives can be reduced to 1-(1H-pyrrol-3-yl)-1H-imidazoles with HCO2NH 4 on Pd/C. The action of KOH on pyrrolylimidazolium salts leads to a new type of stable ylide, 3-(1H-imidazol-3-ium-3-yl)-pyrrol-1-ides, which can, in principle, be in tautomeric equilibrium with the corresponding N-heterocyclic carbene. Although, according to the DFT B3LYP/6-31G(d) calculations in vacuo, electron-donating substituents in the 2-aryl-group cause the tautomeric equilibrium to shift to the carbene side, the investigated compounds exist in the ylide form in solution and in the solid state, which is in agreement with the relative stabilities of the species calculated with the PCM solvent model. This journal is {\circledC} the Partner Organisations 2014.",
author = "Khlebnikov, {Alexander F.} and Tomashenko, {Olesya A.} and Funt, {Liya D.} and Novikov, {Mikhail S.}",
year = "2014",
doi = "10.1039/C4OB00865K",
language = "English",
volume = "12",
pages = "6598--6609",
journal = "Organic and Biomolecular Chemistry",
issn = "1477-0520",
publisher = "Royal Society of Chemistry",
number = "34",

}

TY - JOUR

T1 - Simple Approach to Pyrrolylimidazole Derivatives by Azirine Ring Expansion with Imidazolium Ylides

AU - Khlebnikov, Alexander F.

AU - Tomashenko, Olesya A.

AU - Funt, Liya D.

AU - Novikov, Mikhail S.

PY - 2014

Y1 - 2014

N2 - A domino reaction of 2H-azirines with 1-alkyl-3-phenacyl-1H-imidazolium bromides in the presence of Et3N provides a facile route to 1-alkyl-3-(1H-pyrrol-3-yl)-1H-imidazol-3-ium bromides. 1-Benzyl derivatives can be reduced to 1-(1H-pyrrol-3-yl)-1H-imidazoles with HCO2NH 4 on Pd/C. The action of KOH on pyrrolylimidazolium salts leads to a new type of stable ylide, 3-(1H-imidazol-3-ium-3-yl)-pyrrol-1-ides, which can, in principle, be in tautomeric equilibrium with the corresponding N-heterocyclic carbene. Although, according to the DFT B3LYP/6-31G(d) calculations in vacuo, electron-donating substituents in the 2-aryl-group cause the tautomeric equilibrium to shift to the carbene side, the investigated compounds exist in the ylide form in solution and in the solid state, which is in agreement with the relative stabilities of the species calculated with the PCM solvent model. This journal is © the Partner Organisations 2014.

AB - A domino reaction of 2H-azirines with 1-alkyl-3-phenacyl-1H-imidazolium bromides in the presence of Et3N provides a facile route to 1-alkyl-3-(1H-pyrrol-3-yl)-1H-imidazol-3-ium bromides. 1-Benzyl derivatives can be reduced to 1-(1H-pyrrol-3-yl)-1H-imidazoles with HCO2NH 4 on Pd/C. The action of KOH on pyrrolylimidazolium salts leads to a new type of stable ylide, 3-(1H-imidazol-3-ium-3-yl)-pyrrol-1-ides, which can, in principle, be in tautomeric equilibrium with the corresponding N-heterocyclic carbene. Although, according to the DFT B3LYP/6-31G(d) calculations in vacuo, electron-donating substituents in the 2-aryl-group cause the tautomeric equilibrium to shift to the carbene side, the investigated compounds exist in the ylide form in solution and in the solid state, which is in agreement with the relative stabilities of the species calculated with the PCM solvent model. This journal is © the Partner Organisations 2014.

U2 - 10.1039/C4OB00865K

DO - 10.1039/C4OB00865K

M3 - Article

VL - 12

SP - 6598

EP - 6609

JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

SN - 1477-0520

IS - 34

ER -