Download PDF
Synlett 2008(19): 3063-3067  
DOI: 10.1055/s-0028-1087342
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Ligand-Free C-S Bond Formation Catalyzed by Copper(I) Oxide

Hua-Jian Xua, Xiao-Yang Zhaoa, Yao Fu*b, Yi-Si Feng*a
a School of Chemical Engineering, Hefei University of Technology, Hefei, 230009, P. R. of China
b Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. of China
Fax: +86(551)3607476; e-Mail: fuyao@ustc.edu.cn;
Further Information

Publication History

Received 9 August 2008
Publication Date:
12 November 2008 (online)

    Permissions and Reprints All articles of this category

Abstract

An efficient ligand-free Cu2O-catalyzed C-S bond-formation reaction was developed. A large number of diaryl sulfides and alkylaryl sulfides could be rapidly assembled using this new reaction protocol.

Key words

copper(I) oxide - ligand-free - C-S coupling - iodides - thiols

    References and Notes

  • 1a Beletskaya IP. Cheprakov AV. Coord. Chem. Rev.  2004,  248:  2337 
    Google Scholar
  • 1b Deng W. Liu L. Guo Q.-X. Chin.
    J. Org. Chem.  2004,  24:  150 
    Google Scholar
  • 1c Corbet JP. Mignani G. Chem. Rev.  2006,  106:  2651 
    Google Scholar
  • 2a Kosugi M. Ogata T. Terada M. Sano H. Migita T. Bull. Chem. Soc. Jpn.  1985,  58:  3657 
    Google Scholar
  • 2b Dickens MJ. Gilday JP. Mowlem TJ. Widdowson DA. Tetrahedron  1991,  47:  8621 
    Google Scholar
  • 2c Ishiyama T. Mori M. Suzuki A. Miyaura N. J. Organomet. Chem.  1996,  525:  225 
    Google Scholar
  • 2d Zheng N. McWilliams JC. Fleitz FJ. Armstrong JD. Volante RP. J. Org. Chem.  1998,  63:  9606 
    Google Scholar
  • 2e Mann G. Baranano D. Hartwig JF. Rheingold AL. Guzei IA. J. Am. Chem. Soc.  1998,  120:  9205 
    Google Scholar
  • 2f Schopfer U. Schlapbach A. Tetrahedron  2001,  57:  3069 
    Google Scholar
  • 2g Li GY. Angew. Chem. Int. Ed.  2001,  40:  1513 
    Google Scholar
  • 2h Li GY. Zheng G. Noonan AF. J. Org. Chem.  2001,  66:  8677 
    Google Scholar
  • 2i Murata M. Buchwald SL. Tetrahedron  2004,  60:  7397 
    Google Scholar
  • 2j Itoh T. Mase T. Org. Lett.  2004,  6:  4587 
    Google Scholar
  • 2k Mispelaere-Canivet C. Spindler JF. Perrio S. Beslin P. Tetrahedron  2005,  61:  5253 
    Google Scholar
  • 2l Fernández-Rodríguez MA. Shen Q. Hartwig JF. Chem. Eur. J.  2006,  12:  7782 
    Google Scholar
  • 2m Fernández-Rodríguez MA. Shen Q. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  2180 
    Google Scholar
  • 2n Barbiéri RS. Bellato CR. Dias AKC. Massabni AC. Catal. Lett.  2006,  109:  171 
    Google Scholar
  • 3a Yee Kwong F. Buchwald SL. Org. Lett.  2002,  4:  3517 
    Google Scholar
  • 3b Savarin C. Srogl J. Liebeskind LS. Org. Lett.  2002,  4:  4309 
    Google Scholar
  • 3c Wu YJ. He H. Synlett  2003,  1789 
    Google Scholar
  • 3d Ley SV. Thomas AW. Angew. Chem. Int. Ed.  2003,  42:  5400 
    Google Scholar
  • 3e Deng W. Zou Y. Wang YF. Liu L. Guo QX. Synlett  2004,  1254 
    Google Scholar
  • 3f Bates CG. Saejueng P. Doherty MQ. Venkataraman D. Org. Lett.  2004,  6:  5005 
    Google Scholar
  • 3g Wang YF. Zhou Y. Wang JR. Liu L. Guo Q.-X. Chin. Chem. Lett.  2006,  17:  1283 
    Google Scholar
  • 3h Zhu D. Xu L. Wu F. Wan B. Tetrahedron Lett.  2006,  47:  5781 
    Google Scholar
  • 3i Lv X. Bao W. J. Org. Chem.  2007,  72:  3863 
    Google Scholar
  • 3j Carril M. SanMartin R. Domínguez E. Tellitu I. Chem. Eur. J.  2007,  13:  5100 
    Google Scholar
  • 3k Verma AK. Singh J. Chaudhary R. Tetrahedron Lett.  2007,  48:  7199 
    Google Scholar
  • 3l Rout L. Saha P. Jammi S. Punniyamurthy T. Eur. J. Org. Chem.  2008,  4:  640 
    Google Scholar
  • 3m Kabir MS. van Linn ML. Monte A. Cook JM. Org. Lett.  2008,  10:  3363 
    Google Scholar
  • 4a Zhang Y. Ngeow KN. Ying JY. Org. Lett.  2007,  9:  3495 
    Google Scholar
  • 4b Saxena A. Kumar A. Mozumdar S. Appl. Catal. A.  2007,  317:  210 
    Google Scholar
  • 4c Jammi S. Barua P. Rout L. Saha P. Punniyamurthy T. Tetrahedron Lett.  2008,  49:  1484 
    Google Scholar
  • 5 Wong YC. Jayanth TT. Cheng CH. Org. Lett.  2006,  8:  5613 
    CrossrefPubMedGoogle Scholar
  • 6a Correa A. Carril M. Bolm C. Angew. Chem. Int. Ed.  2008,  47:  2880 
    Google Scholar
  • 6b Correa A. Mancheño OG. Bolm C. Chem. Soc. Rev.  2008,  37:  1108 
    Google Scholar
  • 7 Lindley J. Tetrahedron  1984,  40:  1433 
    CrossrefGoogle Scholar
  • 8 Bates CG. Gujadhur RK. Venkataraman D. Org. Lett.  2002,  4:  2803 
    CrossrefPubMedGoogle Scholar
  • 9a Ranu BC. Saha A. Jana R. Adv. Synth. Catal.  2007,  349:  2690 
    Google Scholar
  • 9b Rout L. Sen TK. Punniyamurty T. Angew. Chem. Int. Ed.  2007,  46:  5583 
    Google Scholar
  • 9c Sperotto E. van Klink GPM. de Vries JG. van Koten G. J. Org. Chem.  2008,  73:  5625 
    Google Scholar
10

General Experimental Procedure
All reagents and solvents were pure analytical-grade materials purchased from commercial sources and were used without further purification. The ¹H NMR and ¹³C NMR spectra were recorded in CDCl3 on a 300 MHz instrument with TMS as internal standard. High-resolution mass spectra (HRMS) were determined on a Micromass GCT-MS mass spectrometer. Thin-layer chromatography was carried out with 0.2 mm thick SiO2 plates (GF254). The columns were hand packed with silica gel 60 (200-300). All reactions were carried out in a Schlenk tube equipped with a magnetic stir bar under Ar atmosphere. A Schlenk tube was charged with Cu2O (0.05 mmol), KOH (2 mmol) and solid substrate, if present. Then, liquid reagents (aryl or heteroaryl halide, 1 mmol; thiol, 1.1 mmol), solvent (1 mL) were added under Ar. The reaction vessel was closed and placed under stirring in a preheated oil bath at 80 ˚C. The reaction mixture was stirred for 24 h. The resulting suspension was cooled to r.t. and filtered through a pad of filter paper with the help of EtOAc (10 mL). The filtrate was concentrated and the residue was purified by silica gel chromatography.
(4-Methoxyphenyl)phenylsulfane (Entry 2, Table 1)
¹H NMR (300 MHz, CDCl3): δ = 3.78 (s, 3 H), 6.98 (d, J = 8.7 Hz, 2 H), 7.17-7.21 (m, 5 H), 7.40 (d, J = 9.0 Hz,
2 H) ppm. ¹³C NMR (75 MHz, CDCl3): δ = 55.2, 115.0, 124.2, 125.7, 128.2, 128.9, 135.3, 138.6, 159.8 ppm. HRMS: m/z calcd for C13H12OS: 216.0609; found: 216.0613.
Phenyl( p -tolyl)sulfane (entry 20, Table 1)
¹H NMR (300 MHz, CDCl3): δ = 2.31 (s, 3 H), 7.09-7.29 (m, 9 H) ppm. ¹³C NMR (75 MHz, CDCl3): δ = 21.1, 126.4, 129.0, 129.8, 130.1, 131.4, 132.3, 137.2, 137.5 ppm. HRMS: m/z calcd for C13H12S: 200.0660; found: 200.0652.

11

No Cu was found in pure diphenylsulfane (entry 4, Table  [¹] ) with X-radial fluorescence-spectrum determining.