Passage des phosphorinènes aux hexadiényl-3,5-phosphines: un nouveau type de coordinat P(III)-diène pour les métaux de transition

Abstract

The reaction of tertbutyllithium with 1-phenylphosphorinan-4-one yields a mixture of isomeric alcohols which are partly separated as their P-sulfides. This mixture is dehydrated by P4S10 to afford 1-phenyl-4-tertbutylphosphorin-3-ene sulfide. This sulfide with nickelocene and allyl iodide gives a P(III) → Ni(II) complex which reacts with P(OMe)3 to yield a methylphenylphosphorinenium salt. This salt with BuLi and cyclohexanone gives the corresponding open chain product, i.e. a hexa-3,5-dienylphosphine oxide. This oxide is reduced by HSiCl3 to the corresponding phosphine which is characterized as its P → Fe(CO)4 complex. The phosphorinene sulfide is metalated on C(2) by n-butyllithium in THF. The lithium derivative with acetone yields a mixture of 'cis' and 'trans' alcohols which are separated and fully characterized. Significant variations of 2J(H–P), 3J(H–P) coupling constants and ν(OH), ν(P=S) ir frequencies are observed between the two isomers. The mixture of 'cis' and 'trans' alcohols is dehydrated to give a endo-exocyclic diene which is not isomerized when reacted with Fe3(CO)12. A reduction-complexation of the P=S group is observed instead. The 2-lithio-phosphorinene is also reacted with iodine to afford a bridged dimer.