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24.2.11.1.4.3 Variation 3: Peterson Reactions

DOI: 10.1055/sos-SD-024-00481

Dölling, W.Science of Synthesis, (200624477.

The deprotonation of 2-(trimethylsilyl)-1,3-dithiane with butyllithium in tetrahydrofuran affords 2-lithio-2-(trimethylsilyl)-1,3-dithiane, which can be used as a reagent for the synthesis of α-silyl ketones.[‌110‌,‌111‌] However, reactions with aldehydes and ketones are normally rapid and lead to ketene S,S-acetals 54 [R3,R3=(CH2)3] as the first isolable products (Scheme 21). This efficient process has been used to synthesize a large number of ketene S,S-acetals from 2-lithio-2-(trimethylsilyl)-1,3-dithiane as well as from the lithium salts of other trimethylsilylated disulfanylmethanes.[‌76‌,‌112‌‌123‌] The carbonyl compounds employed include aromatic and aliphatic ketones, enolizable aldehydes and ketones, α,β-unsaturated aldehydes and ketones, and sterically hindered ketones; some examples are depicted in Scheme 21.

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