可见光促进的苯硫酚与三氟甲基苯砜的三氟甲基化反应。

Visible-light-promoted -trifluoromethylation of thiophenols with trifluoromethyl phenyl sulfone.

作者信息

Wei Zhiqiang, Lou Zhengzhao, Ni Chuanfa, Zhang Wei, Hu Jinbo

机构信息

Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, China.

School of Physical Science and Technology, ShanghaiTech University 100 Haike Road, Shanghai 201210, China.

出版信息

Chem Commun (Camb). 2022 Sep 8;58(72):10024-10027. doi: 10.1039/d2cc03921d.

DOI:10.1039/d2cc03921d

PMID:35983787

Abstract

Trifluoromethyl phenyl sulfone is traditionally a nucleophilic trifluoromethylating agent. Herein, we report the first example of the use of trifluoromethyl phenyl sulfone as a trifluoromethyl radical precursor. Arylthiolate anions can form electron donor-acceptor (EDA) complexes with trifluoromethyl phenyl sulfone, which can undergo an intramolecular single electron transfer (SET) reaction under visible light irradiation, thus realizing the -trifluoromethylation of thiophenols under photoredox catalyst-free conditions. Similar -perfluoroethylation and -perfluoro--propylation of thiophenols are also achieved using the corresponding perfluoroalkyl phenyl sulfones.

摘要

三氟甲基苯砜传统上是一种亲核三氟甲基化试剂。在此，我们报道了首例将三氟甲基苯砜用作三氟甲基自由基前体的实例。芳硫醇阴离子可与三氟甲基苯砜形成电子供体-受体（EDA）配合物，该配合物在可见光照射下可发生分子内单电子转移（SET）反应，从而在无光氧化还原催化剂的条件下实现硫酚的α-三氟甲基化。使用相应的全氟烷基苯砜也可实现硫酚类似的α-全氟乙基化和α-全氟-n-丙基化。