An electrochemical radical Truce Smiles rearrangement of N‐allylbenzamides is documented herein. The selective 1,4‐aryl migration was triggered by the radical fluoromethylation of the alkene providing a direct route to fluoro derivatives of the highly privileged β‐arylethylamine pharmacophore. This practical transformation utilizes readily available starting materials and employs an electrical current to drive the oxidative process under mild reaction conditions. It accommodates a variety of migratory aryl groups with different electronic properties and substitution patterns. Careful selection of the protecting group on the nitrogen atom of the N‐allylbenzamide is crucial to outcompete the undesired 6‐endo cyclization and achieve high level of selectivity towards the 1,4‐aryl migration. DFT calculations support the reaction mechanism and unveil the origin of selectivity between the two competitive pathways.

中文翻译：

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通过 N-烯丙基苯甲酰胺的自由基氟甲基化进行电化学驱动的 1,4-芳基迁移：直接获得功能化 β-芳基乙胺

本文记录了 N-烯丙基苯甲酰胺的电化学自由基 Truce Smiles 重排。选择性 1,4-芳基迁移是由烯烃的自由基氟甲基化引发的，为高度优先的 β-芳基乙胺药效基团的氟代衍生物提供了直接途径。这种实际的转化利用容易获得的起始材料，并采用电流在温和的反应条件下驱动氧化过程。它容纳各种具有不同电子特性和取代模式的迁移芳基。仔细选择 N-烯丙基苯甲酰胺氮原子上的保护基对于战胜不需要的 6-内环化并实现对 1,4-芳基迁移的高选择性至关重要。 DFT 计算支持反应机制并揭示了两种竞争途径之间选择性的起源。