Issue 5, 2016

Synthesis of the first metal-free phosphanylphosphonate and its use in the “phospha–Wittig–Horner” reaction

Abstract

The synthesis of the first phophanylphosphonate, Mes*PH–PO(OEt)2 (2-H), in which the P(III) centre is not coordinated by a M(CO)5 (M = W, Mo, Cr) fragment is reported. The title compound reacts with LDA under the formation of 2-Li which is best described as the enolate form with a high double bond character between the two phosphorus centres. 2-Li is shown to engage in the phospha–Wittig–Horner reaction and converts aldehydes into phosphaalkenes that are metal-free and thus available for future manipulations at the phophorus lone pair. Using a selection of aldehydes with aliphatic, aromatic or vinylic substituents as substrates, phosphaalkene formation proceeds in high yields and high E-selectivity. The selectivity is however compromised during purification on standard silica which was found to promote E/Z isomerization.

Graphical abstract: Synthesis of the first metal-free phosphanylphosphonate and its use in the “phospha–Wittig–Horner” reaction

Supplementary files

Article information

Article type
Paper
Submitted
21 Қыр. 2015
Accepted
26 Қаз. 2015
First published
09 Қар. 2015

Dalton Trans., 2016,45, 2201-2207

Author version available

Synthesis of the first metal-free phosphanylphosphonate and its use in the “phospha–Wittig–Horner” reaction

K. Esfandiarfard, A. I. Arkhypchuk, A. Orthaber and S. Ott, Dalton Trans., 2016, 45, 2201 DOI: 10.1039/C5DT03686K

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