Thioketones carbophilic addition

Reformatsky reagents were shown to undergo carbophilic addition with a variety of thiocarbonyl compounds (thioketones, dithioesters, trithiocarbonates and xanthates). Elimination of sulfur (or of an alkylthio group) led to the formation of carbon-carbon double (or single) bonds [448]. Typically ... 

As mentioned before, it was with thioketones that the first cases of thiophilic addition were evidenced, but many other modes of reaction have been observed concurrently carbophilic addition, reduction, coupling, double addition, and enethiolization [357]. We will not discuss these reactions here, which have not been used much for synthetic purposes. 

On the whole, reactions of thioketones with vinyl-, allyl-, propargyl-, benzyl-, and, sometimes, methylmagnesium halides proceed by carbophilic addition [1-3] (though subsequent rearrangements to the thiophilic product may occur [2]) ... 

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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