N -Activation of 2-PySO 2 CF 2 H for Electrophilic Difluoromethylthiolation of Electron-Rich Heteroarenes

作者：Zhenhao Zhang, Dexun Fu, Yi Luo, Qiqiang Xie, Mingyou Hu, Chuanfa Ni, Jinbo Hu · 发表于：Organic Letters · 年份：2025 · DOI：10.1021/acs.orglett.5c01431 · 被引用次数：3 · 研究领域：Fluorine in Organic Chemistry、Inorganic Fluorides and Related Compounds

Difluoromethyl 2-pyridyl sulfone (2-PySO 2 CF 2 H) is a readily accessible, cost-effective, and versatile reagent with broad applications in fluoroalkylation and fluoroolefination. Here, we unveil a novel application of 2-PySO 2 CF 2 H in electrophilic difluoromethylthiolation. Key to this advance is the strategic N -activation of 2-PySO 2 CF 2 H to generate stable N -methylpyridinium salt and pyridine N -oxide derivatives. When synergistically combined with (EtO) 2 P(O)H/TMSCl, these activated sulfones facilitate efficient difluoromethylthiolation of electron-rich heteroarenes, such as indoles and pyrroles. This research not only introduces a new strategy for electrophilic difluoromethylthiolation but also provides new insights into the mechanism of (EtO) 2 P(O)H/TMSCl-mediated difluoromethylthiolation reactions.