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DOI: 10.1055/s-2006-926235
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
Publication History
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
- 1
Krief A.Dumont W.Robert M. Chem. Commun. 2005, 2167 -
2a
Shah A.Pike VW.Widdowson DA. J. Chem. Soc., Perkin Trans. 1 1997, 2463 -
2b
Kitamura T.Matsuyuki J.Taniguchi J. Synthesis 1994, 147 -
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.
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3b
We found that diphenyliodonium tetrafluoroborate and diphenyliodonium chloride also allow, under identical experimental conditions, the arylation of hexylthiolate (79% and 64% yield, respectively).
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3c
Thiophenol has been previously arylated with diaryl iodonium salts in the presence of tributylamine to produce directly triaryl sulfonium salts. [3d]
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3d
Crivello JV.Lam JHW. Synth. Commun. 1979, 151 -
5a
Reaction performed under argon.
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5b
Reaction initiated after sonication and bubbling argon into the solution.
- 7
Lockhart TP. J. Am. Chem. Soc. 1983, 105: 1940 - 8
Crivello JV.Lam JHW. J. Am. Chem. Soc. 1978, 43: 3055 -
9a
Breckenridge JG.Lewis RW.Quick LA. Can. J. Res. Sect. B 1939, 17: 258 -
9b
Hoste J. Anal. Chim. Acta 1950, 4: 23
References and Notes
We have proved in many instances that iodobenzene is formed as a by-product in these reactions (70-84% isolated yield).
6Those reactions are being investigated in detail and will be reported in the full paper.
10We 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.