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Updated: Jan 17, 2026

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Phospha-Peterson reactions with esters and thioesters: isolation of phosphaalkenes bearing C-heteroatom substituents
Aaron A Mitchell1, Paul A Heine1, Joseph Chang1
1Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1, Canada. dgates@chem.ubc.ca.
Abstract:
Several phospha-Peterson routes to phosphaalkenes from silylphosphines and various ester or thioester reagents are investigated. Treatment of MesP(SiMe3)2 with PhCO(OPh) in the presence of KOH (10 mol%) affords the Becker-type phosphaalkene, MesPC(OSiMe3)Ph rather than MesPC(OPh)Ph. Using stoichiometric Li[MesPSiMe3] rather than catalytic KOH permitted isolation of the presumptive phospha-enolate intermediate following ester cleavage, MesPC(OLi)Ph. The analogous MesPC(ONa)Ph was obtained by treating a mixture of MesPH2 and NaOt-Bu with PhC(O)Cl. Both are dimers in the solid-state. Treatment of the rare alkali metal phospha-enolates with Me3SiCl afforded known MesPC(OSiMe3)Ph. When using ε-thiocaprolactone, OCS(CH2)5, as the substrate in the Lewis acid-mediated phospha-Peterson reaction with ArP(SiMe3)2, three new C-chalcogen-substituted phosphaalkenes, RPCS(CH2)5 (R = Mes, m-Xyl, Tripp) were obtained.
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