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A one‐pot synthesis of functionalized thiopyran derivatives via a Cu‐catalyzed multicomponent reaction of sulfonyl azides, arylacetylenes and dipotassium 2,2‐dicyanoethylene‐1,1‐dithiolate, generated from malononitrile and CS2, has been developed. When alkylacetylenes were used as the terminal alkynes, N‐(alkanethioyl)‐N‐(2,2‐dicyanoethanethioyl)methanesulfonamides were obtained in good yields.
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