First ever observation of the intermediate of phosphonium salt and ylide hydrolysis: P-hydroxytetraorganophosphorane

Byrne, Peter A.; Ortin, Yannick; Gilheany, Declan G.

First ever observation of the intermediate of phosphonium salt and ylide hydrolysis: P-hydroxytetraorganophosphorane

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ByrneGilheanyYlideHydrolysis_9_(corrected).pdf(365.27 KB)

Accepted version

Date

2014-11-26

Authors

Byrne, Peter A.

Ortin, Yannick

Gilheany, Declan G.

Publisher

Royal Society of Chemistry (RSC)

Published Version

10.1039/c4cc08644a

Abstract

P-Hydroxytetraorganophosphorane, the long-postulated intermediate in phosphonium salt and ylide hydrolysis, has been observed and characterised by low temperature NMR, finally definitively establishing its involvement in these reactions. The results require modification of the previously accepted mechanism for ylide hydrolysis: P-hydroxy-tetraorganophosphorane is generated directly by 4-centre reaction of ylide with water.

Keywords

Nuclear magnetic resonance , P-31 NMR spectroscopy , Wittig reaction , Alkaline hydrolysis , Phosphine oxides , Heteroarylphosphorus compounds , Topological representation , Nucleophilic displacement , Substitution reactions , Equilibrium acidities

Citation

Byrne, P. A., Ortin, Y. and G. Gilheany, D. (2015) 'First ever observation of the intermediate of phosphonium salt and ylide hydrolysis: P-hydroxytetraorganophosphorane', Chemical Communications, 51(6), pp. 1147-1150. doi: 10.1039/c4cc08644a