Arylacetonitrile Meets Benzyl Bromide: Isothiouronium‐Mediated α‐Olefination Strategy for 2,3‐Diarylacrylonitriles

2,3‐Diphenylacrylonitriles are widely used in synthetic and medicinal chemistry and have attracted considerable attention for their accessibility. Their synthetic approaches primarily employ metal‐catalyzed coupling reactions between arylacetonitriles and alcohols. Herein, we present an attractive strategy for the synthesis of ( Z )‐2,3‐diarylacrylonitrile derivatives by acceptorless cross‐dehydrogenative coupling between arylacetonitrile and benzyl bromide through isothiouronium salts. This α‐olefination method is operationally simple and proceeds under open‐air, metal‐free conditions. With a broader substrate scope and high product yields, the developed protocol offers a useful strategy for synthesizing acrylonitrile derivatives for further academic and industrial exploration.