Synthesis of all-cis-3-(2-diphenylphosphinoethyl)-1,2,4-tris(diphenylphosphinomethyl)cyclopentane (Ditricyp) from dicyclopentadiene

A new tetraphosphine, all-cis-3-(2-diphenylphosphinoethyl)-1,2,4-tris(diphenylphosphinomethyl)cyclopentane (Ditricyp), has been synthesised in seven steps from commercially available dicyclopentadiene. The ozonolysis of dicyclopentadiene occurred first on the double bond of the bicycloheptene moiety. A very high chemoselective ozonolysis was observed at −60 °C leading to the diol after reductive treatment. From this diol, cis,cis,cis-3-(2-hydroxyethyl)-1,2,4-tri(hydroxymethyl)cyclopentane was obtained after a second ozonolysis. Mesylation and substitution with Ph2PLi led to the title tetradiphenylphosphine Ditricyp. The efficiency of this new tetraphosphine ligand for palladium-catalysed coupling reactions has been studied. Satisfactory results in terms of substrate/catalyst ratio have been obtained for Suzuki, Negishi and Sonogashira couplings and also for Heck vinylation reaction. After chromatographic separation, one enantiomer of this ligand associated to palladium was able to induce enantioselective allylic alkylation with modest enantiomeric excess.