Sulfenate esters, allenyl 2,3 -rearrangements

The addition of an allyl alcohol to racemic allenyl sulfoxides results in vinyl ethers with the sulfinyl moiety at C-1 that undergo sigmatropic rearrangements upon distillation to produce 2,4-dienones after ehmination of sulfenic acid. In one example, an isomeric vinyl ether was obtained with a sulfinyl methyl substituent at C-2 that gave rise to a sulfinyl enone upon rearrangement [138]. In related work, the addition-elimination of an allyl alkoxide to a functionalized vinyl sulfoxide results in a sulfinyl enol ether that rearranges with loss of sulfenic acid to the unsaturated ester [139-141] (Scheme 21). 

In an analogous reaction to that of sulfenates, unsaturated esters of P compounds rearrange easily (equation 24) to corresponding allyl- and allenyl-phosphoryl compounds because the strong heteroatom-oxygen double bond is formed (Scheme 31). ... 

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