.ALPHA.,.BETA.-Epoxy sulfoxides as useful intermediates in organic synthesis. X. An improved synthesis of .ALPHA.-.BETA.-unsaturated carbonyl compounds from carbonyl compounds with carbon homologation through .ALPHA.,.BETA.-epoxy sulfoxides.

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Treatment of the α,β-epoxy sulfoxides derived from ketones and chloromethyl phenyl sulfoxide or 1-chloroalkyl phenyl sulfoxides with lithium perchlorate in the presence of tributylphosphine oxide in toluene at 110 °C for about 1–3 h gave α,β-unsaturated aldehydes or α,β-unsaturated ketones in high yields. In contrast to these results, the α,β-epoxy sulfoxides derived from aldehydes did not give the desired α,β-unsaturated ketones. In this case, a sequential treatment of the α,β-epoxy sulfoxides with benzenethiolate and m-chloroperbenzoic acid afforded α-phenylsulfinylated ketones, which were heated in toluene at 110 °C to give the desired enones in good overall yields. The oxidation of the α,β-unsaturated aldehydes obtained by this method gave α,β-unsaturated carboxylic acids in high yields. These procedures afforded a new method for the synthesis of α,β-unsaturated carbonyl compounds, including α,β-unsaturated esters, from carbonyl compounds with carbon homologation.
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