Allyl vinyl sulphide rearrangement

A tracer study of the mechanism of the rearrangement of thiolsulphinate with acetic anhydride using 13C and lsO has been carried out by Oae and coworkers194. A deuterium isotope effect study of the mechanism of the reactions of singlet oxygen with allylic and vinylic sulphides,... 

A detailed paper on the thermal rearrangements of allyl perchloro-vinyl sulphides has now appeared. Heating (32) to 100-120°(S led to mixtures of (33) and (34) in proportions indicated in the figures. The products were isolated by column chromatography and preparative gas chromatography. Diasteromeric mixtures of (33) were obtained. Treatment of (33a,c,d) with potassium t-butdxide gave (35). 

The Wittig rearrangement of allyl vinyl and benzyl vinyl ethers brought about by strong bases is not shown by benzyl vinyl sulphides. Base-catalysed rearrangement of bis(propargyl) sulphides involves first the formation of the... 

Sigmatropic rearrangements of allyl sulphonium allyl ylides (75) provide the basis of a repetitive one-pot ring-expansion sequence" for 2-vinyl thiocyclic compounds (Scheme 50). A paper" and a section in a review article" have described the utilization of allyl thiol dianions and allyl sulphide anions in carbonyl group umpolung . 

Corey has reported a novel method for the introduction of two alkyl appendages at the carbonyl carbon of ketones. Ketones react with the anion of diethyl allylthiomethylphosphonate (155) to give vinyl allyl sulphides such as (156) heating in the presence of mercury(ii) oxide induces a thio-Claisen rearrangement to yield the aldehyde (157), which can be further elaborated by various oxidation-reduction sequences to give, for example, the spiro-enone (158). 

Addition of thiols to diketen gives y-alkylthio-jS-butyrolactones, which suffer rearrangement, or loss of CO2 to give the allyl sulphide. Radical addition of thiophenol to the allenes (12) and (12a) gives vinyl and allyl sulphides (13) and (14), respectively." The radical pathway is normally... 

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