title: 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.
authors.affiliation: Department of Chemistry-Ångström Laboratories, Uppsala University, Box 523, SE-751 20, Uppsala, Sweden. anna.arkhypchuk@kemi.uu.se sascha.ott@kemi.uu.se.
authors.forename: Keyhan
authors.initials: K
authors.lastname: Esfandiarfard
authors.forename: Anna I
authors.initials: AI
authors.lastname: Arkhypchuk
authors.forename: Andreas
authors.initials: A
authors.lastname: Orthaber
authors.forename: Sascha
authors.initials: S
authors.lastname: Ott