近日，天津大学马军安团队实现了电子供体-受体配合物催化烯烃过渡-无金属三组分硫-三氟甲基化。2025年7月1日，《中国化学》杂志发表了这一成果。

烯烃的过渡金属无硫三氟甲基化代表了快速生成富含C（sp³）的脂肪族三氟甲基化合物的高效转化。然而，一种统一的方法来实现氧、硫和硒三氟甲基化仍迫在眉睫。

研究组报道了在蓝光照射下，三芳胺催化三组分相邻硫-三氟甲基化烯烃，而不需要过渡金属催化剂。该反应广泛适用于氧、硫和硒亲核试剂，促进模块化获取各种β-三氟甲基醇、醚、硫醚、硫氰酸酯和硒氰酸酯，收率高，区域选择性可预测（61个例子）。此外，研究组还展示了其在天然产物和药物化合物的后期修饰中的应用。初步的机制研究表明，三芳胺和Umemoto试剂之间的催化电子供体-受体（EDA）复合物是实现自由基/极性交叉过程的关键。

附：英文原文

Title: Transition-Metal-Free Three-Component Chalcogen-Trifluoromethylation of Alkenes Enabled by a Catalytic Electron Donor-Acceptor Complex†

Author: Hao-Yan Wu, Xiaodong Tang, Ran Guo, Fa-Guang Zhang, Jun-An Ma

Issue&Volume: 2025-07-01

Abstract: The transition metal-free chalcogen trifluoromethylation of alkenes represents a highly efficient transformation for the rapid generation of C(sp3)-rich aliphatic trifluoromethyl compounds. However, a unified methodology to achieve oxy-, thio-, and seleno-trifluoromethylation remains elusive yet highly desirable. In this study, we report a triarylamine-catalyzed three-component vicinal chalcogen-trifluoromethylation of alkenes under blue light irradiation without the need of transition metal catalyst. This reaction is broadly applicable to oxy, thio, and seleno nucleophiles, facilitating modular access to a diverse array of β-trifluoromethyl alcohols, ethers, thioethers, thiocyanates, and selenocyanates with good yields and predictable regioselectivities (61 examples). Additionally, we demonstrate its application in the late-stage modification of natural products and pharmaceutical compounds. Preliminary mechanistic studies suggest that a catalytic electron donor-acceptor (EDA) complex between triarylamine and the Umemoto reagent is key to enabling the radical/polar crossover process.

DOI: 10.1002/cjoc.70157

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70157