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Abstract
AbstractSulfenate anions are known to act as highly reactive species in the organic arena. Now they premiere as organocatalysts. Proof of concept is offered by the sulfoxide/sulfenate‐catalyzed (1–10 mol %) coupling of benzyl halides in the presence of base to generate trans‐stilbenes in good to excellent yields (up to 99 %). Mechanistic studies support the intermediacy of sulfenate anions, and the deprotonated sulfoxide was determined to be the resting state of the catalyst.
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