Double bond migration in Sallyl systems catalysed by [RuClH(CO)(PPh 3) 3

Abstract

Reactions of Sallyl systems (allyl sulphides of RSallyl type, where R=Et, allyl, Ph, Me 3C, Ph 3C, as well as of allyl phenyl sulphoxide, allyl phenyl sulphone, 2,5-dihydro-1,1-dioxothiophene) with [RuClH(CO)(PPh 3) 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SCHCHCH 3 (R=Me 3C, Z: E=96:4 and Ph 3C, Z: E=92:8), ( E)PhS(O 2)CHCHCH 3 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)(PPh 3) 3] has been isolated and its structure has been resolved. The mechanism of the reaction between Sallyl systems and [RuClH(CO(PPh 3) 3] is proposed.