Illuminating the Path of Rearrangement: Visible Light‐Driven Pd‐Catalyzed Substituted Olefins Synthesis

Abstract Pd‐catalyzed reactions are among the most straightforward and efficient methods to proficiently build Csp 2 ‐Csp 2 bonds. Nevertheless, thermal activation remains mandatory in most cases, which may decrease the compatibility with sensitive functional groups. In this context, improvements of conventional strategies must be an important source of research in order to enhance the applicability of such methods for building complex scaffolds. In this work, we contribute to this aim by implying visible‐light as the sole energy source in a Pd‐catalyzed rearrangement reaction involving N ‐tosylhydrazones and aryl halides. These mild reaction conditions efficiently allow oxidative addition, aryl migration and β ‐hydride elimination at room temperature, allowing the construction of various 1,1’ disubstituted olefins.