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

Synlett

Volumn , Issue 3, 2006, Pages 484-486

  Krief, Alain ^a   Dumont, Willy ^a   Robert, Michael ^a,b  

^a UNIVERSITY OF NAMUR   (Belgium)

^b Fonds Pour la Formation la Recherche dans l'Industrie et dans l'Agriculture   (Belgium)

Author keywords

Arylations; Desulfurization; Selenium; Substitutions; Thiols

Indexed keywords

DIPHENYLIODONIUM SALT; DIPHENYLIODONIUM TRIFLATE; N HEXYL DIPHENYLSULFONIUM TRIFLATE; N HEXYL SELENIDE; N HEXYTHIOL; SELENIDE; THIOL DERIVATIVE; TRIFLUOROMETHANESULFONIC ACID; UNCLASSIFIED DRUG;

ARTICLE; ARYLATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; DESULFURIZATION; SUBSTITUTION REACTION;

EID: 33344468517     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2006-926235     Document Type: Article

References (16)

1. Krief, A.; Dumont, W.; Robert, M. Chem. Commun. 2005, 2167.
2. (a) Shah, A.; Pike, V. W.; Widdowson, D. A. J. Chem. Soc., Perkin Trans. 1 1997, 2463.
3. (b) Kitamura, T.; Matsuyuki, J.; Taniguchi, J. Synthesis 1994, 147.
4. (a) 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.
5. (b) We found that diphenyliodonium tetrafluoroborate and diphenyliodonium chloride also allow, under identical experimental conditions, the arylation of hexylthiolate (79% and 64% yield, respectively).
6. 3d
7. (d) Crivello, J. V.; Lam, J. H. W. Synth. Commun. 1979, 151.
8. We have proved in many instances that iodobenzene is formed as a by-product in these reactions (70-84% isolated yield).
9. (a) Reaction performed under argon.
10. (b) Reaction initiated after sonication and bubbling argon into the solution.
11. Those reactions are being investigated in detail and will be reported in the full paper.
12. Lockhart, T. P. J. Am. Chem. Soc. 1983, 105, 1940.
13. Crivello, J. V.; Lam, J. H. W. J. Am. Chem. Soc. 1978, 43, 3055.
14. (a) Breckenridge, J. G.; Lewis, R. W.; Quick, L. A. Can. J. Res. Sect. B 1939, 17, 258.
15. (b) Hoste, J. Anal. Chim. Acta 1950, 4, 23.
16. 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.