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Synlett 2012; 23(19): 2853-2857
DOI: 10.1055/s-0032-1317518
letter
© Georg Thieme Verlag Stuttgart · New York

8-Hydroxyquinolin-N-oxide-Promoted Copper-Catalyzed C–S Cross-Coupling of Thiols with Aryl Iodides

Kun Su
a   Center of Drug Discovery, Chinese Pharmaceutical University, Nanjing 210009, P. R. of China   Fax: +86(20)32015318   Email: zhangdayong@cpu.edu.cn
b   Laboratory of Regenerative Biology, Guangzhou Institute of Biomedicine and Health, CAS, Guangzhou 510663, P. R. of China   Email: jiang_sheng@gibh.ac.cn
,
Yatao Qiu
b   Laboratory of Regenerative Biology, Guangzhou Institute of Biomedicine and Health, CAS, Guangzhou 510663, P. R. of China   Email: jiang_sheng@gibh.ac.cn
,
Yiwu Yao
b   Laboratory of Regenerative Biology, Guangzhou Institute of Biomedicine and Health, CAS, Guangzhou 510663, P. R. of China   Email: jiang_sheng@gibh.ac.cn
,
Dayong Zhang*
a   Center of Drug Discovery, Chinese Pharmaceutical University, Nanjing 210009, P. R. of China   Fax: +86(20)32015318   Email: zhangdayong@cpu.edu.cn
,
Sheng Jiang*
b   Laboratory of Regenerative Biology, Guangzhou Institute of Biomedicine and Health, CAS, Guangzhou 510663, P. R. of China   Email: jiang_sheng@gibh.ac.cn
› Author Affiliations
Further Information

Publication History

Received: 27 August 2012

Accepted after revision: 10 October 2012

Publication Date:
13 November 2012 (online)

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Abstract

8-Hydroxyquinolin-N-oxide was identified as a superior ligand for CuI-catalyzed C–S coupling reactions of aryl iodides with thiols to afford the corresponding thioethers in excellent yield. The method shows excellent chemoselectivity and high functional-group tolerance in both coupling partners.

Key words

C–S coupling reactions - copper - cross-coupling - 8-hydroxyquinolin-N-oxide - Ullmann reaction

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
  • Supporting Information
 

  • References and Notes


      • For recent contributions on Pd-catalyzed C–S coupling reactions, see:
    • 2a Fernández-Rodríguez MA, Shen Q, Hartwig JF. Chem.–Eur. J. 2006; 12: 7782
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    • 2b Fernández-Rodríguez MA, Shen Q, Hartwig JF. J. Am. Chem. Soc. 2006; 128: 2180
      CrossrefSearch in Google Scholar
  • 5 For recent contributions on Co-catalyzed C–S coupling reactions, see: Wong YC, Jayanth TT, Cheng CH. Org. Lett. 2006; 8: 5613
    CrossrefPubMedSearch in Google Scholar
  • 9 General Experimental Procedure An argon-filled flask was charged with CuI (20 mg, 0.1 mmol, 10 mol%), L5 (32 mg, 0.2 mmol, 20 mol%), Cs2CO3 (652 mg, 2 mmol, and thiophenol (1 mmol). The aryl iodide (1.5 mmol) and DMSO (1 mL) were injected into the flask under argon atmosphere. The contents were then stirred at 80 °C for 24 h. After allowing the mixture to cool to r.t., the mixture was diluted with EtOAc (20 mL) and filtered. The filtrate was washed with H2O (2 × 10 mL). The organic phase was dried with Na2SO4, filtered, and the solvent was removed under vacuum, and the residue was purified by chromatography on silica gel to give the desired aryl sulfide. Spectroscopic Data of the Representative Compounds: (2,4,6-Trimethylphenyl)phenyl Sulfide (3c) 1HNMR (400 MHz, CDCl3): δ = 7.19–7.15 (t, J = 7.60 Hz, 2 H), 7.07–7.01 (m, 3 H), 6.93–6.91 (d, J = 7.60 Hz, 2 H), 2.39 (s, 6 H), 2.32 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 143.7, 139.2, 138.4, 129.3, 128.8, 126.9, 125.5, 124.4, 21.7, 21.1. 3-Pyridyl Phenyl Sulfide (3m) 1HNMR (400 MHz, CDCl3): δ = 8.56–8.55 (s, 1 H), 8.46–8.45 (q, J = 4.8 Hz, 1 H), 7.60–7.58 (d, J = 8.00 Hz, 1 H), 7.39–7.29 (m, 5 H), 7.22–7.19 (q, J = 4.80 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 151.1, 147.8, 137.9, 133.9, 133.6, 131.7, 129.5, 127.8, 123.9. 2-(4-Tolylsulfanyl)phenyl Bromide (3o) 1HNMR (400 MHz, CDCl3): δ = 7.54–7.52 (d, J = 7.6 Hz, 1 H), 7.40–7.38 (d, J = 8.00 Hz, 2 H), 7.23–7.21 (d, J = 8.00 Hz, 1 H), 7.13–7.08 (m, 1 H), 7.00–6.96 (m, 1 H), 6.82–6.79 (dd, J = 7.60 Hz, 1 H), 2.38 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 139.8, 139.0, 134.4, 132.9, 130.5, 128.7, 128.7, 127.7, 126.6, 122.0, 21.3.