We report a highly selective synthesis of dissymmetric S,N-malonates from symmetric dithiomalonates under mild conditions. This reaction was accelerated using a Cu(II) catalyst developed by us. When an aliphatic amine was used as the nucleophile, the amine also worked as a base and accelerated the amination reaction. Kinetic studies indicated that the key step of this reaction is the thermal formation of an acylketene; its stability mainly contributes to the selectivity of the reaction. The synthetic utility of dissymmetric S,N-malonates is also shown by the synthesis of linomide.
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