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

Abstract

The hydrophosphorylation of phenylacetylene with di(aryl)phosphane oxides Ar2P(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 Mes2P(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).