Download PDF
Synlett 2010(19): 2891-2894  
DOI: 10.1055/s-0030-1259012
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Facile Preparation of Aryl Sulfides Using Palladium Catalysis under Mild Conditions

Tatsuo Okauchi*, Kouji Kuramoto, Mitsuru Kitamura
Department of Applied Chemistry, Kyushu Institute of Technology, 1-1 Sensui-cho, Tobata, Kitakyushu, 804-8550, Japan
Fax: +81(93)8843314; e-Mail: okauchi@che.kyutech.ac.jp;
Further Information

Publication History

Received 16 September 2010
Publication Date:
22 October 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

A convenient method for C-S cross-coupling of aryl bromides with various thiols has been developed that involves the use of a 1,1′-bis(diphenylphosphino)ferrocene (DPPF)-ligated palladium complex with N,N-diisopropylethylamine (DIPEA) as the base. This coupling is tolerant of a wide range of functional groups, including hydroxy, amino, cyano, nitro, formyl, and carboxyl groups.

Key words

palladium - thiols - cross-coupling - C-S bond formation - sulfide

    References and Notes

  • 1 Metzner P. Thuillier A. Sulfur Reagents in Organic Synthesis   Katritzky AR. Meth-Cohn O. Rees CW. Academic Press; London: 1994. 
    Google Scholar
  • 2a De Martino G. Edler MC. La Regina G. Coluccia A. Barbera MC. Barrow D. Nicholson RI. Chiosis G. Brancale A. Hamel E. Artico M. Silvestri R. J. Med. Chem.  2006,  49:  947 
    Google Scholar
  • 2b Alcaraz ML. Atkinson S. Cornwall P. Foster AC. Gill DM. Humphries LA. Keegan PS. Kemp R. Merifield E. Nixon RA. Noble AJ. O’Beirne D. Patel ZM. Perkins J. Rowan P. Sadler P. Singleton JT. Tornos J. Watts AJ. Woodland IA. Org. Process Res. Dev.  2005,  9:  555 
    Google Scholar
  • 2c Liu LP. Stelmach JE. Natarajan SR. Chen MH. Singh SB. Schwartz CD. Fitzgerald CE. O’Keefe SJ. Zaller DM. Schmatz DM. Doherty JB. Bioorg. Med. Chem. Lett.  2003,  13:  3979 
    Google Scholar
  • 3 Kondo T. Mitsudo T. Chem. Rev.  2000,  100:  3205 
    CrossrefPubMedGoogle Scholar
  • 4a Migita T. Shimizu T. Asami Y. Shiobara J. Kato Y. Kosugi M. Bull. Chem. Soc. Jpn.  1980,  53:  1385 
    Google Scholar
  • 4b Kosugi M. Shimizu T. Migita T. Chem. Lett.  1978,  13 
    Google Scholar
  • 5a Eichman CC. Stambuli JP. J. Org. Chem.  2009,  74:  4005 
    Google Scholar
  • 5b Dahl T. Tornoe CW. Bang-Andersen B. Nielsen P. Jorgensen M. Angew. Chem. Int. Ed.  2008,  47:  1726 
    Google Scholar
  • 5c Norris T. Leeman K. Org. Process Res. Dev.  2008,  12:  869 
    Google Scholar
  • 5d Lee JY. Lee PH. J. Org. Chem.  2008,  73:  7413 
    Google Scholar
  • 5e Mispelaere-Canivet C. Spindler JF. Perrio S. Beslin P. Tetrahedron  2005,  61:  5253 
    Google Scholar
  • 5f Itoh T. Mase T. Org. Lett.  2004,  6:  4587 
    Google Scholar
  • 6a Jammi S. Barua P. Rout L. Saha P. Punnlyamurthy T. Tetrahedron Lett.  2008,  49:  1484 
    Google Scholar
  • 6b Cao Y.-Q. Zhang Z. Guo Y.-X. Wu G.-Q. Synth. Commun.  2008,  38:  1325 
    Google Scholar
  • 6c Zhang YG. Ngeow KC. Ying JY. Org. Lett.  2007,  9:  3495 
    Google Scholar
  • 6d Millois C. Diaz P. Org. Lett.  2000,  2:  1705 
    Google Scholar
  • 7a Bagley MC. Dix MC. Fusillo V. Tetrahedron Lett.  2009,  50:  3661 
    Google Scholar
  • 7b Haldón E. Álvarez E. Nicasio MC. Pérez PJ. Organometallics  2009,  28:  3815 
    Google Scholar
  • 7c Herrero MT. SanMartin R. Domínguez E. Tetrahedron  2009,  65:  1500 
    Google Scholar
  • 7d Jammi S. Sakthivel S. Rout L. Mukherjee T. Mandal S. Mitra R. Saha P. Punniyamurthy T. J. Org. Chem.  2009,  74:  1971 
    Google Scholar
  • 7e Larsson PF. Correa A. Carril M. Norrby PO. Bolm C. Angew. Chem. Int. Ed.  2009,  48:  5691 
    Google Scholar
  • 7f Prasad DJC. Naidu AB. Sekar G. Tetrahedron Lett.  2009,  50:  1411 
    Google Scholar
  • 7g Rout L. Saha P. Jammi S. Punniyamurthy T. Eur. J. Org. Chem.  2008,  640 
    Google Scholar
  • 7h She J. Jiang Z. Wang YG. Tetrahedron Lett.  2009,  50:  593 
    Google Scholar
  • 7i Xu HJ. Zhao XY. Deng J. Fu Y. Feng YS. Tetrahedron Lett.  2009,  50:  434 
    Google Scholar
  • 7j Xu HJ. Zhao XY. Fu Y. Feng YS. Synlett  2008,  3063 
    Google Scholar
  • 7k Goyot O. Gingras M. Tetrahedron Lett.  2009,  50:  1977 
    Google Scholar
  • 7l Prasad DJC. Seker G. Synthesis  2010,  79 
    Google Scholar
  • 8 Wong Y.-C. Jayanth TT. Cheng C.-H. Org. Lett.  2006,  8:  5613 
    CrossrefPubMedGoogle Scholar
  • 9a Correa A. Carril M. Bolm C. Angew. Chem. Int. Ed.  2008,  47:  2880 
    Google Scholar
  • 9b Wu J.-R. Lin C.-H. Lee C.-F. Chem. Commun.  2009,  4450 
    Google Scholar
  • 10 Reddy VP. Kumar AV. Swapna K. Rao KR. Org. Lett.  2009,  11:  1697 
    CrossrefPubMedGoogle Scholar
  • 11a Alvaro E. Hartwig JF. J. Am. Chem. Soc.  2009,  131:  7858 
    Google Scholar
  • 11b Fernández-Rodríguez MA. Hartwig JF.
    J. Org. Chem.  2009,  74:  1663 
    Google Scholar
  • 11c Fernandez-Rodriguez MA. Shen QL. Hartwig JF. Chem. Eur. J.  2006,  12:  7782 
    Google Scholar
  • 11d Fernandez-Rodriguez MA. Shen QL. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  2180 
    Google Scholar
  • 12 Amatore C. Pflüger F. Organometallics  1990,  9:  2276 
    CrossrefGoogle Scholar
13

Typical Experimental Procedure: To a solution of [Pd2(dba)3] (9.2 mg, 0.010 mmol) and DPPF (11.1 mg, 0.020 mmol) in toluene (1.0 mL) were added bromobenzene (0.11 mL, 1.0 mmol), DIPEA (0.19 mL, 1.1 mmol) and octanethiol (0.17 mL, 1.0 mmol) at r.t. The solution was stirred under reflux for 3 h then cooled to r.t. The reaction was quenched by addition of H2O and extracted with EtOAc (3 × 10 mL), and the combined organic layers were washed with brine, dried (Na2SO4), and filtered. The filtrate was concentrated in vacuo and the residue was purified by flash column chroma-tography on silica gel to afford octyl phenyl sulfide (222.3 mg, quantitative).