Double bond migration in S&z.sbnd;allyl systems catalysed by [RuClH(CO)(PPh3)3]

Reactions of S&z.sbnd;allyl systems (allyl sulphides of R&z.sbnd;S&z.sbnd;allyl type, where R=Et, allyl, Ph, Me3C, Ph3C, as well as of allyl phenyl sulphoxide, allyl phenyl sulphone, 2,5-dihydro-1,1-dioxothiophene) with [RuClH(CO)(PPh3)3] and other ruthenium compounds have been investigated. Double-bond migration was observed in the case of allyl trityl sulphide, allyl t-butyl sulphide and both sulphones, that is, where co-ordinating properties of sulphur were not too strong. High-yielded syntheses of (E)- and (Z)-R&z.sbnd;S&z.sbnd;CH&z.dbnd6;CHCH3 (R=Me3C, Z:E=96:4 and Ph3C, Z:E=92:8), (E)&z.sbnd;Ph&z.sbnd;S(O2)&z.sbnd;CH&z.dbnd6;CHCH3 and 2,3-dihydro-1,1-dioxothiophene from respective allyl systems are described. The binuclear Ru complex, formed in the model reaction of allyl phenyl sulphide with [RuClH(CO)(PPh3)3] has been isolated and its structure has been resolved. The mechanism of the reaction between S&z.sbnd;allyl systems and [RuClH(CO(PPh3)3] is proposed. [Copyright &y& Elsevier]