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Synlett 2003(6): 0829-0832
DOI: 10.1055/s-2003-38749
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Copper-Catalyzed Synthesis of Diaryl Selenide from Aryl Iodide and Diphenyl Diselenide Using Magnesium Metal

Nobukazu Taniguchi*, Tetsuo Onami
Department of Chemistry, Fukushima Medical University, Fukushima, 960-1295, Japan
Fax: +81(24)5483836; e-Mail: taniguti@fmu.ac.jp;
Further Information

Publication History

Received 19 February 2003
Publication Date:
17 April 2003 (online)

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Abstract

Various unsymmetrical diaryl selenides can be synthesized from aryl iodides and diphenyl diselenide by an addition of magnesium metal in the presence of a copper catalyst. This method can exploit efficiently two phenylselenide-molecules generated from diphenyl diselenide under neutral conditions.

Key words

copper catalyst - magnesium - diaryl selenide - aryl iodide - diphenyl diselenide

    References

  • 1a Yang BH. Buchwald SL. J. Organomet. Chem.  1999,  576:  125 
    Search in Google Scholar
  • 1b Marcoux J.-F. Doye S. Buchwald SL. J. Am. Chem. Soc.  1997,  119:  10539 
    Search in Google Scholar
  • 1c Hartwig F. Mann G. J. Org. Chem.  1997,  62:  5413 
    Search in Google Scholar
  • 1d Baranano D. Hartwig JF. J. Am. Chem. Soc.  1995,  117:  2937 
    Search in Google Scholar
  • 1e Kosugi M. Shimizu T. Migita T. Chem. Lett.  1978,  13 
  • 2a Krief A. In Comprehensive Organometallic Chemistry II   Vol. 11:  Abel EW. Stone FGA. Wilkinson G. Pergamon Press Ltd.; New York: 1995.  Chap. 13.
    Search in Google Scholar
  • 2b Organoselenium Chemistry, Topics in Current Chemistry 208   Wirth T. Springer-Verlag; Heidelberg: 2000. 
  • 2c Paulmier C. Selenium Reagents and Intermediates in Organic Synthesis, in Organic Chemistry Series 4   Baldwin JE. Pergamon Press Ltd.; Oxford: 1986. 
  • Some examples of phenylselenation of alkyl halide with stoichiometric metal reagent and diphenyl diselenide are known:
  • 3a Okamoto Y. Yano T. J. Organomet. Chem.  1971,  29:  99 
    CrossrefPubMedSearch in Google Scholar
  • 3b Bao W. Zheng Y. Zhang Y. Zhou J. Thetrahedron Lett.  1996,  37:  9333 
    CrossrefPubMedSearch in Google Scholar
  • 3c Bao W. Zhang Y. Synlett  1996,  1187 
    CrossrefPubMed
  • 3d Nishino YT. Okada M. Kuroki T. Watanabe T. Nishiyama Y. Sonoda N. J. Org. Chem.  2002,  67:  8696 
    CrossrefPubMedSearch in Google Scholar
  • As an example using efficiently diphenyl diselenide, the palladium-catalyzed addition to acetylene compounds has been reported:
  • 4a Kuniyasu H. Ogawa A. Miyazaki S.-i. Ryu I. Kanbe N. Sonoda N. J. Am. Chem. Soc.  1991,  113:  9796 
    Search in Google Scholar
  • 4b Ogawa A. Kuniyasu H. Sato K. Sonoda N. Hirao T. J. Org. Chem.  1997,  62:  8361 
    Search in Google Scholar
  • 5a Suzuki H. Abe H. Osuka A. Chem. Lett.  1981,  151 
  • 5b Gujadhur RK. Venkataruman D. Tetrahedron Lett.  2003,  44:  81 
    Search in Google Scholar
  • 6 Nishiyama Y. Tokunaga K. Sonoda N. Org. Lett.  1999,  1:  1725 
    Search in Google Scholar
  • The preparation of ArMgI from ArI and Mg could not be carried out in DMF:
  • 9a Olah GA. Ohannesian L. Arvanaghi M. Chem. Rev.  1987,  87:  671 
    CrossrefSearch in Google Scholar
  • 9b Organomagnesium Methods in Organic Synthesis   Wakefield BJ. Academic Press; San Diego: 1995. 
    Crossref
  • 12 Back TG. Collins S. Law K.-W. Tetrahedron Lett.  1984,  25:  1689 
    Search in Google Scholar
  • 13 Suzuki H. Abe H. Osuka A. Chem. Lett.  1981,  151 
7

In the experiment of entry 1 in Tables [1] , 97% 2-iodotoluene and 89% diphenyl diselenide were recovered; no other products were obtained at all.

8

The magnesium metal could not reduce diphenyl diselenide under our conditions. In entry 2 in Tables [1] , 97% 2-iodotoluene and 96% diphenyl diselenide were recovered.

10

The reaction between CuI and (PhSe)2 produced a green precipitate. The structure of this compound is now under investigation.

11

Cu(I)SePh could be prepared by refluxing Cu2O and PhSeH in EtOH for 24 h.

14

A typical procedure is given for the reaction of 2-iodotoluene with diphenyl diselenide giving phenyl 2-tolyl selenide (entry 1 in Table [2] ): To a mixture of Cu2O (2.1 mg, 0.015 mmol), magnesium(powder) (14.6 mg, 0.6 mmol), 2,2′-bipyridyl(bpy) (4.6 mg, 0.03 mmol) and DMF (0.5 mL) were added 2-iodotoluene (65.4 mg, 0.3 mmol) and diphenyl diselenide (46.8 mg, 0.15 mmol), and the mixture was stirred at 110 °C for 30 h. After evaporation of the solvent, the residue was dissolved in Et2O. The solution was washed with H2O and sat. NaCl and dried over anhyd MgSO4. Chromatography on silica gel(hexane) gave phenyl 2-tolyl selenide (78.1 mg, 92%). 1H NMR (270 MHz, CDCl3): δ = 2.39 (s, 3 H), 7.06 (t, J = 7.0 Hz, 1 H), 7.15-7.41 (m, 7 H), 7.56-7.62 (m, 1 H). 13C NMR (67.5 MHz): δ = 22.3, 126.7, 127.1, 127.7, 127.8, 129.1, 129.3, 130.2, 131.5, 132.7, 133.6. 77Se (51 MHz): δ = 479.7. 4-Bromophenyl phenyl selenide: 1H NMR (270 MHz, CDCl3): δ = 7.26-7.31 (m, 5 H), 7.35-7.38 (m, 2 H), 7.45-7.48 (m, 2 H). 13C NMR (67.5 MHz): δ = 121.4, 127.7, 129.4, 130.3, 132.3, 133.2, 133.3, 134.2. 77Se (51 MHz): δ = 432.0. Anal. Calcd for C12H9SeBr: C, 46.19; H, 2.91. Found: C, 46.39; H, 3.05. Phenyl 4-trifluoromethylphenyl selenide: 1H NMR (270 MHz, CDCl3): δ = 7.24-7.37 (m, 3 H), 7.40-7.47 (m, 4 H), 7.55-7.58 (m, 2 H). 13C NMR (67.5 MHz): δ = 125.8, 125.8, 125.9, 126.0, 128.5, 128.7, 129.7, 131.0, 134.8. 77Se (51 MHz): δ = 443.1. Anal. Calcd for C13H9F3Se: C, 51.84; H, 3.01. Found: C, 51.69; H, 3.14.