Yucai Tang, Jiaming Huang, Jingyao Liang, Na Long, Jiale Liu, Qiumei Yin, Dongfang Jiang, Hai‐Tao Zhu, Wei-Min He
A K 2 S 2 O 8 -mediated tandem bromination/Truce–Smiles rearrangement/desulfonylation of N -arylsulfonyl acrylamides with sodium bromide has been developed. This reaction exhibits broad functional group compatibility and scalability, delivering structurally diverse β -brominated amides containing a quaternary carbon center in good yields. Mechanistic studies indicated that the formation of bromine radicals represents the crucial step in this radical cascade transformation. This approach provides a complementary and efficient route toward the synthesis of valuable β-brominated amide derivatives.