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Synlett 2011(20): 3041-3045  
DOI: 10.1055/s-0031-1289874
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Efficient Copper-Catalyzed One-Pot Synthesis of Diaryl Thioethers by Coupling of Arylboronic Acids with Potassium Ethyl Xanthogenate under Mild Conditions

Liang Wang*, Wei-You Zhou, Sheng-Chun Chen, Ming-Yang He, Qun Chen
Key Laboratory of Fine Petro-Chemical Technology, Changzhou University, Changzhou 213164, P. R. of China
Fax: +86(519)86330251; e-Mail: liangwang@cczu.edu.cn;
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Publication History

Received 21 August 2011
Publication Date:
11 November 2011 (online)

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Abstract

A simple and environmentally benign one-pot synthesis of diaryl thioethers by coupling of arylboronic acids with potassium ethyl xanthogenate through a double arylation process has been developed. The aryl thiols were generated in situ, and the reactions proceeded smoothly to give the corresponding products in good to excellent yields under very mild conditions.

Key words

diaryl thioethers - arylboronic acids - potassium ethyl xanthogenate - one-pot synthesis - copper-catalyzed

    References and Notes

  • 1a Jones DN. In Comprehensive Organic Chemistry   Barton DH. Ollis DW. Pergamon; New York: 1979. 
    Google Scholar
  • 1b Marcincal-Lefebvre A. Gesquiere JC. Lemer C. J. Med. Chem.  1981,  24:  889 
    Google Scholar
  • 1c Ley SV. Thomas AW. Angew. Chem. Int. Ed.  2003,  42:  5400 
    Google Scholar
  • 1d Kondo T. Mitsudo T. Chem. Rev.  2000,  100:  3205 
    Google Scholar
  • 2 Bierbeek AV. Gingras M. Tetrahedron Lett.  1998,  39:  6283 
    Google Scholar
  • 3 Campbell JR. J. Org. Chem.  1964,  29:  1830 
    Google Scholar
  • 4 Ham J. Yang I. Kang H. J. Org. Chem.  2004,  69:  3236 
    Google Scholar
  • 5a Fernandez-Rodroeguez MA. Shen Q. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  2180 
    Google Scholar
  • 5b Li GY. Zheng G. Noonan AF. J. Org. Chem.  2001,  66:  8677 
    Google Scholar
  • 5c Fernandez-Rodroeguez MA. Hartwig JF. Chem. Eur. J.  2010,  16:  2355 
    Google Scholar
  • 6a Kwong FY. Buchwald SL. Org. Lett.  2002,  4:  3517 
    Google Scholar
  • 6b Bates CG. Gujadhur RK. Venkataraman D. Org. Lett.  2002,  4:  2803 
    Google Scholar
  • 6c Chen Y.-J. Chen HH. Org. Lett.  2006,  8:  5609 
    Google Scholar
  • 6d Kuhn M. Falk FC. Paradies J. Org. Lett.  2011,  13:  4100 
    Google Scholar
  • 7a Correa A. Carril M. Bolm C. Angew. Chem. Int. Ed.  2008,  47:  2880 
    Google Scholar
  • 7b Wu JR. Lin CH. Lee CF. Chem. Commun.  2009,  4450 
    Google Scholar
  • 8 Firouzabadi H. Iranpoor N. Gholinejad M. Adv. Synth. Catal.  2010,  352:  119 
    Google Scholar
  • 9 Ke F. Qu Y. Jiang Z. Li Z. Wu D. Zhou X. Org. Lett.  2011,  13:  454 
    Google Scholar
  • 10 Prasad DJC. Sekar G. Org. Lett.  2011,  13:  1008 
    Google Scholar
  • 11 Park N. Park K. Jang M. Lee S. J. Org. Chem.  2011,  76:  4371 
    Google Scholar
  • 12a Lam PYS. Clark CG. Saubern S. Adams J. Averill KM. Chan DMT. Combs A. Synlett  2000,  674 
    Google Scholar
  • 12b Lam PYS. Clark CG. Saubern S. Adams J. Winters MP. Chan DMT. Combs A. Tetrahedron Lett.  1998,  39:  2941 
    Google Scholar
  • 12c Chan DMT. Monaco KL. Wang RP. Winters MP. Tetrahedron Lett.  1998,  39:  2933 
    Google Scholar
  • 12d Lam PYS. Deudon S. Averill KM. Li R. He MY. Desong P. Clark CG. J. Am. Chem. Soc.  2000,  122:  7600 
    Google Scholar
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Typical Procedure for the Synthesis of Diaryl and Aryl Alkyl Thioethers
A mixture of arylboronic acid (0.75 mmol), CuCl (3.7 mg, 0.0375 mmol), potassium ethyl xanthogenate (120.2 mg, 0.75 mmol), and MeOH (3.0 mL) were taken in a flask at r.t. under N2. The reaction mixture was stirred for a certain time under reflux conditions. After disappearance of arylboronic acid (monitored by TLC), the reaction mixture was allowed to cool down to r.t., KOH (168.3 mg, 3 mmol) and another arylboronic acid or alkyl halide (0.50 mmol for unsym-metrical thioethers, 0.75 mmol for symmetrical diaryl thioethers) were added, and the resulting mixture was further heated for a certain time (monitored by TLC). After reaction, the mixture was extracted with EtOAc and H2O. The organic layer was dried over anhyd Na2SO4, and the solvent was removed under reduced pressure. The crude residue was purified by column chromatography on silica gel using EtOAc-hexanes as eluents to give the corresponding thioethers. All the thioethers are known compounds and identified by comparison of their physical and spectral data with those of authentic samples.
Bis(4-Methoxyphenyl)sulfane (3c)
Colorless oil. ¹H NMR (400 MHz, CDCl3): δ = 3.79 (s, 6 H), 6.81-6.86 (m, 4 H), 7.25-7.30 (m, 4 H). ¹³C NMR (100 MHz, CDCl3): δ = 55.5, 114.9, 127.6, 132.9, 159.1. HRMS: m/z [M + H]+ calcd for C14H15O2S: 247.0793; found: 247.0783.
(3-Methoxyphenyl)(phenyl)sulfane (5g)
Colorless oil. ¹H NMR (400 MHz, CDCl3): δ = 3.73 (s, 3 H), 6.73-6.78 (m, 1 H), 6.83-6.85 (m, 1 H), 6.86-6.90 (m, 1 H), 7.17 (d, J = 8.4 Hz, 1 H), 7.20-7.31 (m, 3 H), 7.33-7.37 (m, 2 H). ¹³C NMR (100 MHz, CDCl3): δ = 55.4, 112.9, 116.0, 123.1, 127.4, 129.4, 130.1, 131.6, 135.4, 137.4, 160.2. HRMS: m/z [M + H]+ calcd for C13H13OS: 217.0687; found: 217.0688.
Benzyl Phenyl Sulfide (Table 4, Entry 1)
White solid; mp 40-42 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 4.11 (s, 2 H), 7.14-7.34 (m, 10 H). ¹³C NMR (100 MHz, CDCl3): δ = 39.2, 126.5, 127.3, 128.6, 128.9, 129.0, 130.0, 136.5, 137.6. HRMS: m/z [M + K]+ calcd for C13H12SK: 239.0297; found: 239.0289.