Synlett 2017; 28(17): 2272-2276
DOI: 10.1055/s-0036-1588482
letter
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Direct Synthesis of Aryl Thiols from Aryl Iodides Using Sodium Sulfide Aided by Catalytic 1,2-Ethanedithiol

Hongyu Xuea, Bing Jinga, Shasha Liua, Junghyun Chae*b, Yajun Liu*a
  • aCollege of Life Science and Medicine, Dalian University of Technology, Panjin 124221, P. R. of China   Email: yjliu85@dlut.edu.cn
  • bDepartment of Chemistry and Research Institute of Basic Sciences, Sungshin Women’s University, Seoul 136-742, South Korea   Email: jchae@sungshin.ac.kr
We gratefully acknowledge the financial support by the Fundamental Research Funds for the Central Universities (DUT15RC(3)043; DUT17LK23), National Research Foundation of Korea (Basic Science Research Program Fund: NRF2015R1D1A1A01060188).
Further Information

Publication History

Received: 21 May 2017

Accepted after revision: 07 June 2017

Publication Date:
18 July 2017 (eFirst)

Abstract

A copper-catalyzed direct and effective synthesis of aryl thiols from aryl iodides using readily available Na2S·9H2O and 1,2-ethanedithiol was described. A variety of aryl thiols were readily obtained in yields of 76–99%. In this protocol, Na2S·9H2O was used as ultimate sulfur source, and 1,2-ethanedithiol functioned as an indispensable catalytic reagent.

Supporting Information

 
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  • 21 General Experimental Procedure for the Synthesis of Aryl Thiols from Aryl Iodides To a test tube containing a magnetic bar was added aryl iodide (1 mmol), copper powder (6.35 mg, 0.1 mmol), Na2S·9H2O (720.54 mg, 3 mmol), and DMSO (2 mL). After flushing with argon, 1,2-ethanedithiol (8.4 μL, 0.1 mmol) was added. The mixture was stirred in the oil bath at 100 °C for 20 h. After cooled to ambient temperature, the reaction mixture was distributed in aq HCl (5%) and EtOAc. The organic layer was separated and washed with water and brine, dried, and concentrated under vacuum. The crude product was further purified by column chromatography using ethyl acetate/n-hexane as eluent to provide the desired aryl thiol. Analytical Data of Representative Compounds 4-Methylbenzenethiol (2a) 19 Yield 97%; white solid. 1H NMR (500 MHz, CDCl3): δ = 7.19 (d, J = 8.1 Hz, 2 H), 7.06 (d, J = 8.0 Hz, 2 H), 3.39 (s, 1 H), 2.31 (s, 3 H). 13C NMR (126 MHz, CDCl3): δ = 135.6, 129.8, 129.8, 126.5, 20.9. 4-Methoxybenzenethiol (2h) 19 Yield 93%; yellow liquid. 1H NMR (500 MHz, CDCl3): δ = 7.18 (d, J = 8.5 Hz, 2 H), 6.72 (d, J = 8.8 Hz, 2 H), 3.70 (s, 3 H), 3.28 (s, 1 H). 13C NMR (126 MHz, CDCl3): δ = 158.5, 132.4, 119.8, 114.7, 55.3. 4-Mercaptobenzoic Acid (2n)19 Yield 99%; white powder. 1H NMR (500 MHz, CDCl3): δ = 7.96 (d, J = 7.5 Hz, 2 H), 7.32 (d, J = 7.6 Hz, 2 H), 3.65 (s, 1 H). 13C NMR (126 MHz, CDCl3): δ = 171.1, 139.8, 130.8, 128.1, 126.1.