Acyl anion equivalents sulfur containing

All known acyl anion equivalents that contain a nucleophilic sulfur atom (unoxidized) open epoxides (e.g., 39-43). Much to our surprise, all known... 

The phenyl sulfides available permit the synthesis of organolithium by reaction (c) (see Table 2), e.g., tertiary alkyllithiums that are not available from the corresponding halides and sulfur-stabilized vinyllithiums that serve synthetically as acyl anion equivalents. Also, the benzyl ether moiety is not cleaved when the substrate contains both this moiety and a thiophenol group, and bis(phenyl sulfides) may be treated with 1-2 equiv of Li metal to give the mono- or dilithiums, respectively. 

Alkylations of Acyl Anion Equivalents Containing at Least One Sulfur or Selenium on their Carbanionic Center... 

Alkylations of sulfur-containing acyl anion equivalents... 

In a different approach, the reactivity of thiazolium salts derived acyl anion equivalents (biological active aldehyde ) toward sulfur electrophiles has been examined recently (329) and provides a model for the thioester-forming step catalyzed by the lipoic acid containing enzymes. The results suggest that the biological generation of thioesters of coenzyme A from a-keto acids occurs via the direct reductive acylation of enzyme-bound lipoic acid by the active aldehyde, as already shown on page 453. 

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