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Herein a novel, elusive cyanotrifluoromethylthiolation of unactivated dialkyl-substituted alkynes is reported. Taking advantage of the intramolecular cyano migration strategy, the reaction proceeds stereoselectively to deliver E-olefinic products. A variety of tetrasubstituted trifluoromethylthiolated acrylonitriles are afforded in modest to good yields.

Graphical abstract: Cyanotrifluoromethylthiolation of unactivated dialkyl-substituted alkynes via cyano migration: synthesis of trifluoromethylthiolated acrylonitriles

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