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

Abstract

A series of tertiary phosphine sulfides and selenides have been synthesized in excellent yields (88‐99%) via a three‐component reaction between secondary phosphines, electron‐rich alkenes (styrene, vinyl chalcogenides), and elemental sulfur or selenium, proceeding under solvent‐free conditions (80‐82°C, 4–44 h). The interaction occurs via initial oxidation of secondary phosphines with elemental sulfur or selenium followed by noncatalyzed anti‐Markovnikov addition of the generated R2P(E)H (E = S, Se) species to alkenes to afford the corresponding adducts with high chemo‐ and regioselectivity.

Recent Advances in Organic Reactions Involving Elemental Sulfur

“…Tertiary alkyl‐ and alkenylphosphine sulfides 555 and 556 are obtained by heating diphenylphosphine 554 with alkenes 553 and alkynes 553 ,, respectively, and elemental sulfur (Scheme ). These simple methods were highly regioselective towards the anti ‐Markovnikov products and diastereoselective towards the Z alkenyl phosphines in the cases of alkyne substrates.…”

1. Introduction of selenium and tellurium into reaction systems

“…The known homopolyselenium cations include Se4 2+ , Se8 2+ , and Se10 2+ , but no applications of these species in synthesis have been reported. The interaction of elemental selenium with phosphines [64] is exemplified by the one-pot synthesis of diselenophosphinic selenoesters [65]. A more detailed discussion of the preparation and application of phosphorus-selenium reagents is presented in Chapter 5.…”

Introduction of selenium and tellurium into reaction systems

“…The interaction of elemental selenium with phosphines [64] is exemplified by the one-pot synthesis of diselenophosphinic selenoesters [65]. A more detailed discussion of the preparation and application of phosphorus-selenium reagents is presented in Chapter 5.…”