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

Haigen Shen; Hawen Xiao; Lin Zhu; Chaozhong Li

doi:10.1055/s-0039-1690187

Synlett, Table of Contents

Synlett 2020; 31(01): 41-44
DOI: 10.1055/s-0039-1690187

cluster – 9th Pacific Symposium on Radical Chemistry

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

Haigen Shen

^aKey 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

^aKey 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∗

^aKey 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∗

^aKey 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

^bSchool 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 Stephenson

Abstract

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Published as part of the Cluster 9^th 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.

Key words

copper - trifluoromethylation - radicals - alkynes - 1,3-enynes

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References

References and Notes

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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.

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