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The review describes thiophilic reactions of thiocarbonyl compounds with C‐ and S‐nucleophiles. They occur more frequently than has been supposed up to now, especially between vicinal thiocarbonyl systems and S‐nucleophiles. A general relation between thiophilic reactions and the redox behaviour of the system and a possibility to estimate approximately the thiophilic properties are discussed. Some conclusions for the synthesis and the behaviour of thiocarbonyl compounds are drawn.

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