Ligand-Free Copper-Catalyzed
Synthesis of Diaryl Thioethers from Aryl Halides and Thioacetamide

Chuanzhou Tao; Aifeng Lv; Nan Zhao; Shuai Yang; Xiaolang Liu; Jian Zhou; Weiwei Liu; Jing Zhao

doi:10.1055/s-0030-1259079

LETTER

Ligand-Free Copper-Catalyzed Synthesis of Diaryl Thioethers from Aryl Halides and Thioacetamide

Chuanzhou Tao*^a,b, Aifeng Lv^b, Nan Zhao^a, Shuai Yang^a, Xiaolang Liu^a, Jian Zhou^a, Weiwei Liu^a, Jing Zhao*^b
^a School of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005, P. R. of China
Fax: +86(518)85895121; e-Mail: cztao@mail.ustc.edu.cn;
^b State Key Laboratory of Pharmaceutical Biotechnology, School of Life Sciences, Nanjing University, Nanjing 210093, P. R. of China
Fax: +86(25)83592672; e-Mail: jingzhao@nju.edu.cn;

Abstract

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Abstract

Diaryl thioethers can be prepared via a copper-catalyzed cross-coupling between aryl halides and thioacetamide using Cs₂CO₃ as a base and DMSO-H₂O as a solvent at 120 ˚C.

Key words

copper - catalysis - cross-coupling - diaryl thioether - arylation - thioacetamide

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References and Notes

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Coupling of Aryl Halides with Thioacetamide - General Procedure An oven-dried Schlenk tube was charged with CuI (18 mg, 10 mol%), MeCSNH₂ (75 mg, 1.0 mmol), Cs₂CO₃ (978 mg, 3.0 mmol), and aryl halide (2.5 mmol). The tube was evacuated and backfilled with argon. Then, DMSO-H₂O (0.5 mL/0.25 mL) were added under argon. The tube was sealed, and the reaction mixture was stirred at 120 ˚C for
24-36 h. The reaction mixture was quenched with H₂O, extracted with Et₂O, and dried over anhyd MgSO₄. The solvents were removed under vacuum, and the residue was purified by column chromatography (silica gel, EtOAc-PE) to afford the product.

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