Acta Chim. Sinica ›› 2017, Vol. 75 ›› Issue (1): 66-69.DOI: 10.6023/A16070341 Previous Articles     Next Articles

Special Issue: 有机光化学



苟宝权, 杨超, 张磊, 夏吾炯   

  1. 哈尔滨工业大学化工与化学学院 城市水资源和环境国家重点实验室 哈尔滨 150080
  • 投稿日期:2016-07-15 修回日期:2016-08-17 发布日期:2016-08-24
  • 通讯作者: 杨超,;夏吾炯,;
  • 基金资助:

    项目受国家自然科学基金(Nos.21272047,21372055 and 21472030)、城市水资源与水环境国家重点实验室(No.2015DX01)和中央高校基础研究(No.HIT.BRETIV.201310)资助.

Visible-Light Induced Trifluoromethylation of Internal Olefinic C-H Bonds through Photoredox Catalysis

Gou Baoquan, Yang Chao, Zhang Lei, Xia Wujiong   

  1. School of Chemistry and Chemical Engineering, State Key Lab of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150080
  • Received:2016-07-15 Revised:2016-08-17 Published:2016-08-24
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21272047, 21372055 and 21472030), State Key Laboratory of Urban Water Resource and Environment (No. 2015DX01) and the Fundamental Research Funds for the Central Universities (No. HIT.BRETIV.201310).

An approach for direct trifluoromethylation of internal olefins of α-oxoketene dithioacetals has been achieved by using Ru(bpy)3Cl2 as photocatalyst and Togni's reagent as trifluoromethylating agent under irradiation with visible light. Under a nitrogen atmosphere, a mixture of α-oxoketene dithioacetal (0.1 mmol), Togni's reagent (0.15 mmol), Ru(bpy)3Cl2 (0.005 mmol), and Na2CO3 (0.3 mmol) in DMSO (1 mL) was stirred at room temperature for 72 h under 5 W Blue LEDS, which led to the trifluoromethylated products in 40%~90% yield. This protocol provides an efficient and easy access to prepare trifluoromethylated dithioalkyl α-oxoketene acetals under mild conditions, and is highlighted by its operational simplicity and avoiding using toxic reagent. Furthermore, the gram-scale reaction of 1a suggested the potential application of this protocol in organic synthesis.

Key words: visible light, olefin, trifluoromethylation, photocatalyst, operational simplicity