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The electrocatalytic reductive transformation of thioamides has been challenging due to catalyst poisoning by sulfur‐containing species. An electrohydrogenative coupling of thioamides with olefins is achieved using a cobalt catalyst, with protons as the hydrogen source. This protocol enables highly selective synthesis of α‐branched amines, including deuterium‐labeled analogues, with excellent functional group tolerance and late‐stage modification. More details are discussed in the article by Liu et al . on pages 2847—2854. image