Synthesis of α‐Aryl Acrylamides via Lewis‐Base‐Mediated Aryl/Hydrogen Exchange

Herein we report a method for the synthesis of α‐aryl acrylamides leveraging polar S‐to‐C aryl migrations induced by a Lewis basic organocatalyst. In contrast to previously reported radical aryl migrations of sulfonyl acrylimides, this polar process enables subsequent elimination, ultimately leading to a formal aryl/hydrogen exchange including SO(2) extrusion. This reaction is selective for electron‐deficient aromatic groups, while tolerating a variety of substituents on nitrogen and in the β‐position, and it delivers useful building blocks for further transformations, including cycloaddition and cyclisation reactions. The mechanism was investigated in detail using quantum chemical calculations, which unexpectedly revealed the Lewis base to be involved in several decisive steps.