Alkylation of delocalized anions resulting from metallation of N-phenyl thioimidoesters (precursors of dithioesters and thiolesters) takes place on nitrogen with “saturated” thioimidoesters (alkane thiomidates). On the contrary, unsaturated thiomidoesters (α or β- ethylenic, α-arylated) are regioselectively alkylated on the α carbon atom by alkyl or allylic halides. The possibilities for synthesis offered by successive uses of the reactivities of ...