Thiophilic additions, organometallic compounds

For a review of additions of organometallic compounds to C=S bonds, both to the sulfur (thiophilic addition) and to the carbon (carbophilic addition), see Warded, J.L. Paterson, E.S. in Hartley Patai The Chemistry of the Metal-Carbon Bond, vol. 2 Wiley NY, 1985, p. 219. See pp. 261-267. 

Many examples of the nucleophilic attack of organometallic compounds at the sulfur atom of thiocarbonyl groups were reported in the 1970s by Beak, Vialle, Ohno, Schaumann and their co-workers [119, 120, 327-329]. This thiophilic addition opens the way for a new method of preparation of carbanions a to sulfur. 

Reactions.—Three interesting papers deal with the reactivity of thioketens. A noteworthy paper by Schaumann and Walter reports that thiophilic addition of organometallic compounds is observed with thioketens. At - 78 °C, dialkyl-thioketens (53) react with phenyl-lithium or methyl-lithium by 1,2>thiophilic addition to give enesulphides (55). At room temperature the main products... 

Reactions of different organometallic species with thiocarbonyi compounds have been extensively investigated and been shown to proceed both in a carbophilic and a thiophilic fashion. However, other reactions can be observed simultaneously such as reduction, double addition, coupling, deprotonation and formation of enesulfides1,226,423. A complex pattern appears in the reactions of thioketones with lithium or Grignard reagents424. The first application of Reformatsky reagents in C—C bond formation by reaction with... 

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