Copper(II)-Promoted Mono-Selective ortho C–H Chlorination of Arenes by Using Trimethyl(trichloromethyl)silane

Zhaobin Zhu; Changming Xu; Yongchang Wang; Li Zhao

doi:10.1055/s-0036-1591542

Synlett, Inhaltsverzeichnis

Synlett 2018; 29(08): 1122-1124
DOI: 10.1055/s-0036-1591542

letter

Copper(II)-Promoted Mono-Selective ortho C–H Chlorination of Arenes by Using Trimethyl(trichloromethyl)silane

Zhaobin Zhu

Lanzhou Jiaotong University, School of Chemical and Biological Engineering, No. 88, Anning West Road, Lanzhou 730070, P. R. of China eMail: xucm@mail.lzjtu.cn

,

Changming Xu*

Lanzhou Jiaotong University, School of Chemical and Biological Engineering, No. 88, Anning West Road, Lanzhou 730070, P. R. of China eMail: xucm@mail.lzjtu.cn

,

Yongchang Wang

Lanzhou Jiaotong University, School of Chemical and Biological Engineering, No. 88, Anning West Road, Lanzhou 730070, P. R. of China eMail: xucm@mail.lzjtu.cn

,

Li Zhao

Lanzhou Jiaotong University, School of Chemical and Biological Engineering, No. 88, Anning West Road, Lanzhou 730070, P. R. of China eMail: xucm@mail.lzjtu.cn

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Abstract

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Abstract

The first example of a Cu-promoted ortho-chlorination of aryl C–H bonds by using TMSCCl₃ as chlorinating agent is reported. This reaction features a high selectivity toward monochlorination over dichlorination, compatibility with a variety of functional groups, and gram-scale synthesis.

Key words

C–H activation - copper - chlorination - trimethyltrichloromethylsilane

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Referenzen

References and Notes
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18 Copper-Promoted Monochlorination of 2-Arylpyridines or 2-Arylpyrimidines 1 with TMSCCl₃; General Procedure A solution of 1 (0.2 mmol), Cu(OAc)₂ (0.2 mmol), TMSCCl₃ (0.4 mmol), and TFA (1.0 mmol) in DCE (2.0 mL) was stirred in a reaction tube under N₂ (1 atm) at 80 °C for 96 h, then cooled to r.t. A 2 M aq solution of NaOH (8.0 mL) was added, and the mixture was extracted with CH₂Cl₂ (3 × 10.0 mL). The organic layers were combined, dried (MgSO₄), and concentrated under vacuum. The crude product was purified by chromatography [silica gel, PE–EtOAc (20:1)]. 2-(2-Chlorophenyl)pyridine (3a) Yellow oil; yield: 27.2 mg (72%). ¹H NMR (400 MHz, CDCl₃): δ = 7.29–7.32 (m, 1 H), 7.32–7.39 (m, 2 H), 7.48 (dd, J = 1.6, 7.2 Hz, 1 H), 7.60 (dd, J = 2.0, 7.6 Hz, 1 H), 7.65 (d, J = 8.0 Hz, 1 H), 7.77 (td, J = 1.6, 7.6 Hz, 1 H), 8.73 (d, J = 4.8 Hz, 1 H). 2-(2,6-Dichlorophenyl) pyridine (4a) Yellow oil; yield: 2.2 mg (5%). ¹H NMR (400 MHz, CDCl₃): δ = 7.26–7.28 (m, 1 H), 7.34–7.37 (m, 2 H), 7.41 (d, J = 8.8 Hz, 2 H), 7.82 (td, J = 2.0, 8.0 Hz, 1 H), 8.76–8.75 (m, 1 H).

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