Scope and Limitations of the s-Block Metal-Mediated Pudovik Reaction

Abstract

The hydrophosphorylation of phenylacetylene with di(aryl)phosphane oxides Ar₂ P(O)H (Pudovik reaction) yields E/Z-isomer mixtures of phenylethenyl-di(aryl)phosphane oxides (1). Alkali and alkaline-earth metal di(aryl)phosphinites have been studied as catalysts for this reaction with increasing activity for the heavier s-block metals. The Pudovik reaction can only be mediated for di(aryl)phosphane oxides whereas P-bound alkyl and alcoholate substituents impede the P-H addition across alkynes. The demanding mesityl group favors the single-hydrophosphorylated products 1-Ar whereas smaller aryl substituents lead to the double-hydrophosphorylated products 2-Ar. Polar solvents are beneficial for an effective addition. Increasing concentration of the reactants and the catalyst accelerates the Pudovik reaction. Whereas Mes₂ P(O)H does not form the bis-phosphorylated product 2-Mes, activation of an ortho-methyl group and cyclization occurs yielding 2-benzyl-1-mesityl-5,7-dimethyl-2,3-dihydrophosphindole 1-oxide (3).

Keywords: Pudovik reaction; catalysis; hydrophosphorylation; phosphane oxide addition; s-block metals.