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Synlett 2018; 29(17): 2279-2282
DOI: 10.1055/s-0037-1610257
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of β-CF3 Ketones through Copper/Silver Cocatalyzed Oxidative Coupling of Enol Acetates with ICH2CF3

Yi Xiong
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P. R. of China   Email: weideng@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
,
De Chen
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P. R. of China   Email: weideng@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
,
Sheng Zeng
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P. R. of China   Email: weideng@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
,
Chaozhihui Cheng
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P. R. of China   Email: weideng@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
,
Pengjie Wang
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P. R. of China   Email: weideng@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
,
Wei Deng*
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P. R. of China   Email: weideng@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
,
Jiannan Xiang*
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P. R. of China   Email: weideng@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
,
Niannian Yi*
b   College of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan, 411104, P. R. of China   Email: yiniannian@hnu.edu.cn
› Author AffiliationsThe work was supported by the Planned Science and Technology ­Project of Hunan Province, China (No. 2015WK3003).
Further Information

Publication History

Received: 06 June 2018

Accepted after revision: 29 July 2018

Publication Date:
22 August 2018 (online)

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Abstract

A simple method for the synthesis of β-CF3 ketones through copper/silver cocatalyzed oxidative coupling of enol acetates with ICH2CF3 has been developed. Enol acetates were chosen as the source of carbonyl group, giving the β-CF3 ketones in moderate yields. Control experiments imply that a radical process maybe involved in this reaction.

Key words

β-CF3 ketone - oxidative coupling - radical reaction - enol ­acetate

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610257.
  • Supporting Information
 

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  • 10 Typical Procedure: To a sealed tube were added enol acetate (0.75 mmol), ICH2CF3 (0.5 mmol, 105 mg), Cu(OAc)2·H2O (0.05 mmol, 10 mg), Ag2SO4 (0.1 mmol, 31 mg), Et3N (0.5 mmol, 50 mg), TBHP (1.5 mmol, 193 mg, 70% in water), and CH3CN (1 mL), then the tube was stirred at 100 °C for 24 h. After completion of the reaction, the resulting mixture was diluted with dichloromethane and washed with water. The separated aqueous phase was washed with CH2Cl2. The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated under vacuo. The crude mixture was purified by column chromatography on silica gel (petroleum ether/ethyl acetate) to afford the desired product 3. 4,4,4-Trifluoro-1-phenylbutan-1-one (3a) Yield: 71 mg (70%); white solid; mp 56–58 °C; 1H NMR (400 MHz, CDCl3): δ = 7.98 (d, J= 7.6 Hz, 2 H), 7.61 (t, J= 7.2 Hz, 1 H), 7.49 (t, J= 7.6 Hz, 2 H), 3.27 (t, J= 7.6 Hz, 2 H), 2.66–2.54 (m, 2 H); 13C NMR (100 MHz, CDCl3): δ = 196.3, 136.1, 133.6, 128.8, 128.0, 127.1 (q, J= 274.2 Hz), 31.2 (d, J= 2.9 Hz), 28.3 (q, J = 29.9 Hz); 19F NMR (376 MHz, CDCl3): δ = –66.45.