Ni‐Catalyzed Reductive Acyl Cross‐Coupling: Straightforward Synthesis of α‐Trifluoromethylthiolated Ketones

Vanderbiest, Xavier;Riant, Olivier
(2026) European Journal of Organic Chemistry — (2026)

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Abstract
The trifluoromethylthiol group (-SCF3) has attracted considerable attention due to its high lipophilicity and strong electron-withdrawing ability. Over the past decades, numerous methodologies have been developed for the construction of C(sp2)–SCF3 bonds through the selective introduction of the SCF3 group into arenes or vinyl derivatives. In contrast, the synthesis of tertiary C(sp3)-SCF3 compounds remains more restricted. Herein, we present a Ni-catalyzed reductive acyl cross-coupling that enables the direct construction of α-trifluoromethylthiolated ketones in a single step utilizing a recently developed SCF3-containing electrophiles. Moreover, mechanistic investigations have demonstrated the presence of an unusual pathway for reductive coupling and the essential role of zinc.
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Vanderbiest, X., & Riant, O. (2026). Ni‐Catalyzed Reductive Acyl Cross‐Coupling: Straightforward Synthesis of α‐Trifluoromethylthiolated Ketones. European Journal of Organic Chemistry. Published. https://doi.org/10.1002/ejoc.70503 (Original work published 2026)