Synlett 2014; 25(09): 1307-1311
DOI: 10.1055/s-0033-1341057
letter
© Georg Thieme Verlag Stuttgart · New York

A Practical Method for Metal-Free Radical Trifluoromethylation of Styrenes with NaSO2CF3

Hai-Qing Luo*
Department of Chemistry & Chemical Engineering, Gannan Normal University, Ganzhou, Jiangxi, 341000, P. R. of China   Fax: +86(797)8393670   Email: luohaiq@sina.com   Email: luoxuzhong@hotmail.com
,
Zhi-Peng Zhang
Department of Chemistry & Chemical Engineering, Gannan Normal University, Ganzhou, Jiangxi, 341000, P. R. of China   Fax: +86(797)8393670   Email: luohaiq@sina.com   Email: luoxuzhong@hotmail.com
,
Wen Dong
Department of Chemistry & Chemical Engineering, Gannan Normal University, Ganzhou, Jiangxi, 341000, P. R. of China   Fax: +86(797)8393670   Email: luohaiq@sina.com   Email: luoxuzhong@hotmail.com
,
Xu-Zhong Luo*
Department of Chemistry & Chemical Engineering, Gannan Normal University, Ganzhou, Jiangxi, 341000, P. R. of China   Fax: +86(797)8393670   Email: luohaiq@sina.com   Email: luoxuzhong@hotmail.com
› Author Affiliations
Further Information

Publication History

Received: 18 January 2014

Accepted after revision: 02 March 2014

Publication Date:
27 March 2014 (online)

Abstract

A mild and practical protocol for the metal-free trifluoromethylation of styrenes using NaSO2CF3 (Langlois reagent) and TBHP was developed. The approach provides efficient access to α-trifluoromethylated ketones and alcohols in moderate to good yields.

Supporting Information

 
  • References and notes

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  • 17 Typical Procedure: To a septum-capped 25 mL sealed tube with a magnetic stirring bar were added CF3SO2Na (1.8 mmol) and BQ (0.3 mmol) in MeCN–H2O (4:1; 4 mL) under O2, followed by the addition of styrene 1a (0.3 mmol) and tBuOOH (2.4 mmol). The sealed tube was screw capped and heated at 80 °C for 16–24 h (oil bath). Upon completion, the mixture was cooled to room temperature and diluted with H2O (10 mL). The aqueous layer was extracted with EtOAc (3 × 10 mL) and the combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by silica gel chromatography (hexane) to provide pure products 2a and 3a in 57% combined yield. Purification by flash column chromatography on silica gel (hexanes–EtOAc, 20:1 v/v) gave the pure products. Compound 2a: Yield: 36%; white solid. 1H NMR (400 MHz, CDCl3): δ = 7.87 (d, J = 7.4 Hz, 2 H), 7.57 (t, J = 7.4 Hz, 1 H), 7.44 (t, J = 7.6 Hz, 2 H), 3.73 (q, J = 10.0 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 189.7 (q, J = 2.8 Hz), 135.7, 134.1, 128.9, 128.3, 124.0 (q, J = 276.7 Hz), 41.9 (q, J = 28.3 Hz). 19F NMR (376 MHz, CDCl3): δ = –62.1 (t, J = 10.0 Hz, 3F). Compound 3a: Yield: 21%; colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.32–7.41 (m, 5 H), 7.08 (dd, J = 9.0, 3.6 Hz, 1 H), 2.56–2.70 (m, 1 H), 2.39–2.52 (m, 1 H), 2.25 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ = 142, 128.9, 128.4, 125.9 (q, J = 275.7 Hz), 125.7, 68.8 (d, J = 3.3 Hz), 42.9 (q, J = 26.9 Hz). 19F NMR (376 MHz, CDCl3): δ = –63.7 (t, J = 10.5 Hz, 3F). HRMS (EI): m/z [M + H]+ calcd. for C9H10F3O: 191.0684; found: 191.0688.