Catalyst- and solvent-free regiospecific S N H Ar phosphinylation of pyridines with H -phosphinates mediated by benzoylphenylacetylene.

Autor: Khrapova KO; A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk 664033, Russian Federation. boris_trofimov@irioch.irk.ru., Volkov PA; A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk 664033, Russian Federation. boris_trofimov@irioch.irk.ru., Telezhkin AA; A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk 664033, Russian Federation. boris_trofimov@irioch.irk.ru., Albanov AI; A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk 664033, Russian Federation. boris_trofimov@irioch.irk.ru., Chupakhin ON; I.Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, 22/20 S. Kovalevskoi/Akademicheskaya St., Ekaterinburg 620219, Russian Federation., Trofimov BA; A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk 664033, Russian Federation. boris_trofimov@irioch.irk.ru.
Jazyk: angličtina
Zdroj: Organic & biomolecular chemistry [Org Biomol Chem] 2024 Jul 03; Vol. 22 (26), pp. 5419-5427. Date of Electronic Publication: 2024 Jul 03.
DOI: 10.1039/d4ob00661e
Abstrakt: Pyridines undergo a facile S N H Ar phosphinylation with H -phosphinates under catalyst- and solvent-free conditions (50-55 °C) in the presence of benzoylphenylacetylene to afford 4-phosphinylpyridines in up to 68% yield. In this reaction, benzoylphenylacetylene activates the pyridine ring by the formation of a 1,3(4)-dipolar complex, deprotonates H -phosphinates to generate P-centered anions and finally acts as an oxidizer, being eliminated from an intermediate ion pair. Terminal electron-deficient acetylenes (methyl propiolate and benzoylacetylene) are inefficient as mediators in the above S N H Ar process.
Databáze: MEDLINE
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