127901-19-3Relevant academic research and scientific papers
Reactivity of lithium diphenylphosphonium diylides towards phosphorus electrophiles: Synthesis of α,β-unsaturated phosphorus compounds
Taillefer, Marc,Cristau, Henri Jean,Fruchier, Alain,Vicente, Virginie
, p. 307 - 315 (2001)
The study of the reactivity of non-stabilized, semi-stabilized and stabilized lithium diphenylphosphonium diylides 1-4 towards Ph2PCl, allowed the synthesis of various α,β-unsaturated phosphines 13-14, via the intermediate formation of the corresponding functionalized monoylides 9-10 and their in situ reaction with carbonyl compounds. In many cases, the reaction is Z-stereoselective and the created double bond can be di- or also trisubstituted. The precise 1H-NMR study of the phosphines 13a-d and the X-ray analysis of 13a (Z isomer) allowed us to assign without ambiguity the stereochemistry of these compounds and to solve a 1H-NMR question. Contrary to reported results in the literature for 13a, we have shown that for the double bond of this phosphine, there is no exception to the general rule 3JHH(trans) > 3JHH(cis). The extension of this reactivity study to other phosphorus electrophiles such as Ph2P(O)Cl, Ph2P(S)Cl and (EtO)2P(O)Cl allowed, as preliminary results, the E-stereoselective synthesis of styrylphosphine oxide and sulfide and diethyl styrylphosphonate.
Stereo-controlled synthesis of styrylphosphines and their oxides or sulfides using phosphonium diylides
Taillefer,Cristau
, p. 7857 - 7860 (1998)
Lithium dimethyldiphenylphosphonium diylide reacts with electrophiles such as Ph2PCl, Ph2P(O)Cl or Ph2P(S)Cl to give monoylide intermediates allowing by reaction with benzaldehyde the synthesis of the styrylphosphines or the corresponding oxides or sulfides. This efficient one-pot method permits at choice the selective synthesis of each isomer Z or E and corroborates further the isomeric identification of the styrylphosphines.
