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 SO2 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. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Citation

Miran Lemmerer, Haoqi Zhang, Anthony J Fernandes, Tobias Fischer, Marianne Mießkes, Yi Xiao, Nuno Maulide. Synthesis of α-Aryl Acrylamides via Lewis-Base-Mediated Aryl/Hydrogen Exchange. Angewandte Chemie (International ed. in English). 2022 Aug 29;61(40):e202207475

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PMID: 35881564

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