Persistent Radical Cation Catalysis Enables Radical-Polar Crossover Cycloisomerization of Unactivated Alkenes to CF 3 -Heterocycles

作者：Rui Zhu, Ya-Zhen Zeng, Chi Zhang, Lei Jin, Man‐Yi Han, Peng Wang, Saihu Liao · 发表于：Organic Letters · 年份：2025 · DOI：10.1021/acs.orglett.5c03659 · 被引用次数：2 · 研究领域：Radical Photochemical Reactions、Sulfur-Based Synthesis Techniques、Catalytic C–H Functionalization Methods

Saturated heterocycles are privileged pharmacophores, yet their synthetic development is often limited by a narrow substrate scope and metal dependence. We describe a metal-free photochemical strategy catalyzed by a persistent radical cation (PTH •+ ) that facilitates cycloisomerization via oxidative radical-polar crossover (ORPC). This approach converts CF 3 •-derived alkyl radicals into alkylsulfonium intermediates as masked carbocations, enabling efficient synthesis of CF 3 -functionalized γ-butyrolactones and tetrahydrofurans in 25–85% yields. The reaction features broad substrate compatibility, including challenging radicals, and proves to be effective in late-stage modification of bioactive molecules, highlighting its potential for complex heterocycle synthesis.