Reaction of Vinyl Selenides with Secondary Phosphines and Elemental Selenium: One‐Pot Selective Synthesis of a New Family of Diselenophosphinic Se‐Esters

Abstract

Alkyl vinyl selenides react with diverse secondary phosphines and elemental selenium in a 1.1:1:2 molar ratio (120–124°C, 20–40 min, 1,4‐dioxane) to afford selectively earlier unknown diselenophosphinic Se‐esters, R2P(Se)SeCH(Me)SeR´, in 82–99% yield. This three‐component atom‐economic reaction proceeds via intermediate formation of diselenophosphinic acid R2P(Se)SeH (generated from secondary phosphine and selenium), which adds to the double bond of vinyl selenide in a Markovnikov manner to give the target products.

Straightforward Solvent‐Free Synthesis of Tertiary Phosphine Chalcogenides from Secondary Phosphines, Electron‐Rich Alkenes, and Elemental Sulfur or Selenium

“…Common side products of the reaction, according to 31 P NMR monitoring, are dichalcogenophosphinates, R 1 2 P(E)ECH(Me)R 2 (E = S, Se), forming in up to 10 mol% via previously reported a three‐component reaction , in which 2 equiv of elemental chalcogen is employed (Scheme ). In this reaction, in situ generation of dichalcogenophosphinic acids R 1 2 P(E)EH (from secondary phosphines and elemental S or Se) takes place; the further addition of which to alkenes gives the esters of dichalcogenophosphinic acids .…”