Angewandte Chemie, Accepted Article.
Dealkenylative alkenylation of alkene C(sp3)‐C(sp2) bonds has been an unexplored area for C‐C bond formation. Herein, we report 64 examples of β‐alkylated styrene derivatives synthesized through the reactions of readily accessible feedstock olefins with β‐nitrostyrenes through ozone/Fe(II)‐mediated radical substitution. These reactions proceed with good efficiency and high stereoselectivity under mild conditions and tolerate an array of functional groups. We demonstrate the applicability of the strategy through several synthetic transformations of the products, as well as the syntheses of the natural product iso‐moracin and the drug ( E )‐metanicotine.