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Unexpected Decarbonylation of Acylethynylpyrroles under the Action of Cyanomethyl Carbanion: A Robust Access to Ethynylpyrroles
It has been found that the addition of CH(2)CN(−) anion to the carbonyl group of acylethynylpyrroles, generated from acetonitrile and t-BuOK, results in the formation of acetylenic alcohols, which undergo unexpectedly easy (room temperature) decomposition to ethynylpyrroles and cyanomethylphenylketo...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9919934/ https://www.ncbi.nlm.nih.gov/pubmed/36771055 http://dx.doi.org/10.3390/molecules28031389 |
Sumario: | It has been found that the addition of CH(2)CN(−) anion to the carbonyl group of acylethynylpyrroles, generated from acetonitrile and t-BuOK, results in the formation of acetylenic alcohols, which undergo unexpectedly easy (room temperature) decomposition to ethynylpyrroles and cyanomethylphenylketones (retro-Favorsky reaction). This finding allows a robust synthesis of ethynylpyrroles in up to 95% yields to be developed. Since acylethynylpyrroles became available, the strategy thus found makes ethynylpyrroles more accessible than earlier. The quantum-chemical calculations (B2PLYP/6-311G**//B3LYP/6-311G**+C-PCM/acetonitrile) confirm the thermodynamic preference of the decomposition of the intermediate acetylenic alcohols to free ethynylpyrroles rather than their potassium derivatives. |
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