Formation and Reactivity of Phosphorus–Selenium Rings

Abstract

Lawesson reagent for selenium fans: Phosphorus selenium heterocycles and, in particular, [PhPSe(2)](2) (known as Woollins' reagent) are proving valuable in the synthesis of new heterocycles and for the insertion of selenium into organic substrates. Incorporation of phosphorus and selenium atoms into the products leads to a surprising variety of structures.Phosphorus-selenium ring chemistry has developed to include the synthesis of some exciting new motifs and provided organic chemists with a new reagent, [PhPSe(2)](2), which has become known as Woollins' reagent.

How Not to Discover a New Reagent. The Evolution and Chemistry of Woollins' Reagent

“…In the following there is a summary of different reaction types but no discussion of metal complex formation though Rothenberger has developed direct reactions of WR with metal salts to good effect 49 and we have carried out some studies relating to our earlier work on ZDDP. 50 We have reviewed the reactivity of WR previously 51,52 and in the following provide a brief summary together with more recent results.…”

Organophosphorus‐Selenium Heteroatom Derivatives from Selenation of Primary/Secondary Amines and Haloalkanes/Dihaloalkanes

“…11 The reactions of WR with various organic substrates exhibit a diverse spectrum ranging from simple oxygen-selenium exchange to the formation of complex phosphorus-selenium heterocycles as well as the formation of surprising phosphorus-selenium-free products. [12][13][14][15][16][17][18][19][20][21][22][23][24][25] We recently have reported the synthesis of a series of ammonium phenylphosphonamidodiselenoates and phenylphosphonamidodiselenoic diamides from the reaction of WR with primary or secondary amines, 26 and the formation of a series of organo phosphorus-selenium heteroatom derivatives from the selenation of alkenyl or arynyl-diamines. 27 As a part of our continuous exploration into the reactivity of WR towards different organic nucleophiles, herein, we report the synthesis of a series of novel Se-alkylphenylphosphonamidodiselenoates and alkane bis(Nalkyl-P-phenylphosphonamidodiselenoate)s via the reaction of WR with primary/secondary amines, followed by the in situ treatment with haloalkanes or dihaloalkanes.…”

Ammonium Phenylphosphonamidodiselenoates and Phenylphosphonamidodi‐selenoic Diamides from the Selenation of Primary and Secondary Amines

“…[8] Reactions of Woollins' reagent with organic substrates display a wide spectrum ranging from simple oxygen-selenium exchange to the formation of complex phosphorus-selenium heterocycles as well as surprising phosphorus-selenium-free products. [9][10][11][12][13][14][15][16][17] Herein, as part of our investigation into the reactivity of Woollins' reagent towards different organic substrates, we report the synthesis of a series of novel ammonium phenylphosphonamidodiselenoates and phenylphosphonamidodiselenoic diamides from the selenation of primary/secondary amines, the complex of Cd 2 L 4 (L = [Se 2 PPh(NCH(CH 3 ) 2 ] -) and three representative related single crystal X-ray structures. To the best of our knowledge this is the first reported synthesis and characterization of ammonium phenylphosphonamidodiselenoates and phenylphosphonamidodiselenoic diamides and the representative coordination compound, providing a valuable addition to the library of phosphodiselenoate compounds known.…”