Allyl Sulphides and Selenides

Yamamoto, H. Yatagai, and K. Maruyama, y. Chem. Soc., Chem. Commun., 1979, 157 Chem. 

Kinetics of the oxidation of diallyl sulphide by singlet oxygen, and its inhibition by rubrene, have been reported. Isomerization studies in which the base-catalysed prop-2-eny 1-prop-1-enyl equilibrium for allyl sulphides, sulphoxides, and sulphones were compared have been undertaken, and isolated reports on this topic have been rationalized in terms of electronic distribution in the functional groups. 

The cleavage of C—S bonds that accompanies the cross-coupling of allyl sulphides with a Grignard reagent combined with NiCl2 and PPhj leads to mixtures of alkenes. 

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Sulphonium ylides are in certain cases unstable and they undergo further transformation affording useful final products. In this way allylic sulphides and selenides were used to transfer an alkylthio- or alkylseleno-group onto the a-carbon of / -dicarbonyl compounds in the form of their ylides the sequence of reactions were a transylidation followed by [2,3]-sigmatropic rearrangement. 

Reductive cleavage of sulphides, selenides, and tellurides on Raney nickeP and cleavage by lithium in THE, leading to secondary or tertiary alkyl-lithium compounds, are useful synthetic operations novel variations are involved in the cleavage of dialkenyl sulphides with EtjSiH (giving low yields of silyl sulphides) and of alkenyl, aryl, and allyl sulphides and selenides with PPhj and... 

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