Synlett 2020; 31(01): 41-44
DOI: 10.1055/s-0039-1690187
cluster – 9th Pacific Symposium on Radical Chemistry
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Radical Bis(trifluoromethylation) of Alkynes and 1,3-Enynes

Haigen Shen
a  Key Laboratory of Organofluorine Chemistry and Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China   Email: zhulin@mail.ustc.edu.cn   Email: clig@mail.sioc.ac.cn
,
Hawen Xiao
a  Key Laboratory of Organofluorine Chemistry and Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China   Email: zhulin@mail.ustc.edu.cn   Email: clig@mail.sioc.ac.cn
,
Lin Zhu
a  Key Laboratory of Organofluorine Chemistry and Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China   Email: zhulin@mail.ustc.edu.cn   Email: clig@mail.sioc.ac.cn
,
Chaozhong Li
a  Key Laboratory of Organofluorine Chemistry and Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China   Email: zhulin@mail.ustc.edu.cn   Email: clig@mail.sioc.ac.cn
b  School of Materials and Chemical Engineering, Ningbo University of Technology, No. 201 Fenghua Road, Ningbo 315211, P. R. of China
› Author Affiliations

Subject Editor: David Nicewicz and Corey StephensonThis project was supported by the Natural Science Foundation of Shanghai (Grant Number 16ZR1443700), by the National Natural Science Foundation of China (Grant Numbers 21421002, 21532008, 21602239, and 21871285), by the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant Number XDB20020000), and by the Shanghai Scientific and Technological Innovation Project (Grant Number 18JC1410600).
Further Information

Publication History

Received: 12 July 2019

Accepted after revision: 05 August 2019

Publication Date:
15 August 2019 (online)


Published as part of the Cluster 9th Pacific Symposium on Radical Chemistry

Abstract

The copper-catalyzed radical bis(trifluoromethylation) of alkynes and 1,3-enynes is described. With Cu(CH3CN)4BF4 as the catalyst, the reaction of arylalkynes with Togni reagent II and (bpy)Zn(CF3)2at room temperature affords the corresponding 1,2-bis(trifluoromethylated) alkenes in good yields with excellent E-stereoselectivity. Under similar conditions, the reaction of 1,3-enynes provides the corresponding 1,4-bis(trifluoromethylated) allenes exclusively in satisfactory yields. The protocol exhibits broad substrate scope and excellent functional group compatibility.

Supporting Information

 
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  • 19 Typical Procedure for the 1,2-Bis(trifluoromethylation) of Alkynes To a 25 mL sealed tube were added Cu(CH3CN)4BF4 (19 mg, 20 mol%), Togni reagent II (161 mg, 0.51 mmol), and bpyZn(CF3)2 (162 mg, 0.45 mmol). The mixture was evacuated and backfilled with argon (3×). Alkyne 1a (54 μL, 0.3 mmol) and anhydrous CH3CN (6.0 mL) were then added successively. The reaction mixture was stirred at room temperature for 12 h. The resulting mixture was diluted with DCM and filtered through a pad of Celite. After the removal of solvent under reduced pressure, the crude product was purified by column chromatography on silica gel with petroleum ether as the eluent to give the (E)-1,2- bis(trifluoromethylated) product 2a as a colorless oil; yield 72 mg (81%).
  • 20 (E)-1-(tert-Butyl)-4-(1,1,1,4,4,4-hexafluorobut-2-en-2-yl)benzene (2a) 1H NMR (400 MHz, CDCl3): δ = 7.43 (d, J = 7.6 Hz, 2 H), 7.22 (d, J = 8.4 Hz, 2 H), 6.47 (q, J = 7.2 Hz, 1 H), 1.34 (s, 9 H). 13C NMR (100 MHz, CDCl3): δ = 153.0, 141.4 (qq, J = 30.7, 4.5 Hz), 128.4, 125.9, 125.3, 122.5 (qq, J = 35.2, 6.3 Hz), 122.0 (q, J = 273.5 Hz), 121.6 (q, J = 270.9 Hz), 34.7, 31.2. 19F NMR (376 MHz, CDCl3): δ = –58.00 (d, J = 6.8 Hz, 3 F), –68.25 (s, 3 F). IR (neat): ν = 2964, 2927, 2872, 1270, 1185, 1147, 1023, 832, 646 cm-1. EIMS: m/z (rel. intensity) = 296 (20) [M+], 281 (100), 253. HRMS: m/z calcd for C14H14F6 [M]: 296.1000; found: 296.0999.