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Please login or sign up for a free trial to access the full content. 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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Me Me (MM8)8 8888 [‌888‌,‌888‌,‌888‌]
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M (MM8)8 88 [‌888‌]
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MM=M(Me)8 Me (MM8)8 88 [‌88‌,‌888‌]
MM=MMMe M (MM8)8 8888 [‌888‌,‌888‌,‌888‌]
M(MMe)=MM8 M (MM8)8 88 [‌888‌]
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eeeeeeeeee M (MM8)8 88 [‌88‌,‌888‌]
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Meeeeeeeeeee Meeeeeeee

Meeeee M,M-Meeeeee 88; Meeeeee Meeeeeeee:[‌88‌,‌888‌‌888‌]

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