Catalyst-Free Phosphorylation of Acridine with Secondary Phosphine Chalcogenides: Nucleophilic Addition vs SNHAr Reaction

Pavel A Volkov; Kseniya O Khrapova; Anton A Telezhkin; Nina I Ivanova; Alexander I Albanov; Nina K Gusarova; Boris A Trofimov

doi:10.1021/acs.orglett.8b03061

Catalyst-Free Phosphorylation of Acridine with Secondary Phosphine Chalcogenides: Nucleophilic Addition vs S_N^HAr Reaction

Org Lett. 2018 Dec 7;20(23):7388-7391. doi: 10.1021/acs.orglett.8b03061. Epub 2018 Nov 16.

Authors

Pavel A Volkov¹, Kseniya O Khrapova¹, Anton A Telezhkin¹, Nina I Ivanova¹, Alexander I Albanov¹, Nina K Gusarova¹, Boris A Trofimov¹

Affiliation

¹ A.E. Favorsky Irkutsk Institute of Chemistry , Siberian Branch of the Russian Academy of Sciences , 1 Favorsky St. , Irkutsk 664033 , Russian Federation.

PMID: 30444374
DOI: 10.1021/acs.orglett.8b03061

Abstract

Acridine adds secondary phosphine chalcogenides HP(X)R₂ (X = O, S, Se; R = Ar, ArAlk) under catalyst-free conditions at 70-75 °C (both in the presence and absence of the electron-deficient acetylenes) to give 9-chalcogenophosphoryl-9,10-dihydroacridines in 61-94% yields. This contrasts with pyridines, which under similar conditions undergo an S_N^HAr reaction, wherein electron-deficient acetylenes play the role of oxidants. For acridine, the S_N^HAr step has been accomplished by the oxidation of the intermediate 9-phosphoryl-9,10-dihydroacridines (X = O) with chloranil.

Publication types

Research Support, Non-U.S. Gov't