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Synlett 2006(3): 0484-0486  
DOI: 10.1055/s-2006-926235
LETTER
© Georg Thieme Verlag Stuttgart · New York

Arylation of n-Hexylthiol and n-Hexyl Phenyl Sulfide Using Diphenyl­iodonium Triflate: Synthetic and Mechanistic Aspects - Application to the Transformation of n-Hexylthiol to n-Hexylselenide

Alain Krief*a, Willy Dumonta, Michael Roberta,b
a Laboratoire de Chimie Organique de Synthèse, Facultés Universitaires N.-D. de la Paix, 61 rue de Bruxelles, Namur 5000, Belgium
Fax: +32(81)724536; e-Mail: alain.krief@fundp.ac.be;
b , Fonds pour la Formation à la Recherche dans l’Industrie et l’Agriculture, 5 rue d’Egmont, Bruxelles 1000, Belgium
Further Information

Publication History

Received 9 December 2005
Publication Date:
06 February 2006 (online)

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Abstract

n-Hexyl diphenylsulfonium triflate has been efficiently prepared from n-hexylthiol and diphenyliodonium triflate and has been efficiently transformed to n-hexyl selenide.

Key words

arylations - thiols - desulfurization - selenium - substitutions

    References and Notes

  • 1 Krief A. Dumont W. Robert M. Chem. Commun.  2005,  2167 
    Crossref
  • 2a Shah A. Pike VW. Widdowson DA. J. Chem. Soc., Perkin Trans. 1  1997,  2463 
    Thieme Connect
  • 2b Kitamura T. Matsuyuki J. Taniguchi J. Synthesis  1994,  147 
    Thieme Connect
  • 3a

    Arylation of n-hexylthiol has been also achieved in toluene by in situ formation of the corresponding thiolate using either potassium (18% yield of 3a) or better cesium (65% yield of 3a) hydroxide.
  • 3b

    We found that diphenyliodonium tetrafluoroborate and diphenyliodonium chloride also allow, under identical experimental conditions, the arylation of hexylthiolate (79% and 64% yield, respectively).
  • 3c

    Thiophenol has been previously arylated with diaryl iodonium salts in the presence of tributylamine to produce directly triaryl sulfonium salts. [3d]

  • 3d Crivello JV. Lam JHW. Synth. Commun.  1979,  151 
  • 5a

    Reaction performed under argon.

  • 5b

    Reaction initiated after sonication and bubbling argon into the solution.

  • 7 Lockhart TP. J. Am. Chem. Soc.  1983,  105:  1940 
    CrossrefSearch in Google Scholar
  • 8 Crivello JV. Lam JHW. J. Am. Chem. Soc.  1978,  43:  3055 
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  • 9a Breckenridge JG. Lewis RW. Quick LA. Can. J. Res. Sect. B  1939,  17:  258 
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  • 9b Hoste J. Anal. Chim. Acta  1950,  4:  23 
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4

We have proved in many instances that iodobenzene is formed as a by-product in these reactions (70-84% isolated yield).

6

Those reactions are being investigated in detail and will be reported in the full paper.

10

We found that Cu(I) triflate is a poorer catalyst for the arylation of n-hexyl phenyl sulfide (3a) using diphenyliodonium tetrafluoroborate (4a) instead of the corresponding triflate 4b (4a:3a:CuOTf ratio: 1:1:5):
(i) 110 °C, 0.2 h, 5a: 72%, 3a: 24% or (ii) 80 °C, 1.5 h, 5a: 13%, 3a: 73%; compare to Scheme [3] , Table [1] , entries e
and g.