First example of the $$ C_{sp^2 } $$ -P bond formation in the reaction of red phosphorus with hetaryl halides

Abstract

Direct reactions of red and white phosphorus with electrophiles (aryland hetarylalkenes, arylacetylenes, alkyl, allyl, and benzyl halides) in superbasic systems alkali metal hydroxide – dipolar aprotic solvent (DMSO, HMPTA) or under the conditions of phase transfer catalysis are now considered as a novel chlorine-free method of formation of the С–P bond [1, 2]. Within this approach, the one-pot methods have been elaborated for the synthesis of various phosphines, phosphine oxides, and phospinic acids [1, 2] which had earlier been obtained by multistep processes from phosphorus halides. However, in the case of the substitution reaction only the Сsp3–P bond was formed. Recently, tris(1-naphthyl)phosphine was synthesized from red phosphorus and 1-naphthyl bromide in the system KОН–DMSO [3]. To the best of our knowledge, there are no data in the literature on the formation of the Сsp2–P in the reactions of elemental phosphorus with hetaryl halides in superbasic systems.