Synthesis of the first metal-free phosphanylphosphonate and its use in the "phospha-Wittig-Horner" reaction
2016 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 45, no 5, 2201-2207 p.Article in journal (Refereed) PublishedText
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.
Place, publisher, year, edition, pages
2016. Vol. 45, no 5, 2201-2207 p.
IdentifiersURN: urn:nbn:se:uu:diva-280913DOI: 10.1039/c5dt03686kISI: 000369413700046PubMedID: 26574885OAI: oai:DiVA.org:uu-280913DiVA: diva2:912302
FunderSwedish Research Council