Solvent-Tuned Photocatalytic (Phenylsulfonyl)difluoromethylation of Anilines: Selectivity and Postfunctionalization

作者：Hang Zhang, Xiao Long, Huanyi Guo, Guoliang Pu, Yuhang Zhang, Jiarui Liang, Pan Wang, Qiuli Yao, Chun‐Yang He · 发表于：Organic Letters · 年份：2025 · DOI：10.1021/acs.orglett.5c04618 · 被引用次数：3 · 研究领域：Fluorine in Organic Chemistry、Radical Photochemical Reactions、Sulfur-Based Synthesis Techniques

The control of the ortho versus para selectivity in substitution reactions of aniline derivatives remains a fundamental challenge in organic synthesis. Herein, we report a photoredox-catalyzed synthesis of (phenylsulfonyl)difluoromethylated anilines. The ortho – para selectivity of this transformation is predominantly governed by the solvent choice. Using the reaction system with a 1:1 DMSO/DMA mixed solvent achieves a high para: ortho ratio of up to 13.3:1. Conversely, switching to a 2:1 MeOH/DCM mixture as the solvent enables the ortho isomer to be obtained highly selectively, even as the sole product. The practicality of this protocol is further evidenced by its application in diverse derivative syntheses. For example, the PhSO 2 CF 2 group can be converted into CF 3 or CF 2 H and the amino group can be transformed into iodo or alkynyl groups, among others.