Synlett 2006(9): 1351-1354  
DOI: 10.1055/s-2006-939707
LETTER
© Georg Thieme Verlag Stuttgart · New York

Aryl- or Alkylation of Diaryl Disulfides Using Organoboronic Acids and a Copper Catalyst

Nobukazu Taniguchi*
Department of Chemistry, Fukushima Medical University, Fukushima 960-1295, Japan
Fax: +81(24)5471369; e-Mail: taniguti@fmu.ac.jp;
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Publikationsverlauf

Received 1 February 2006
Publikationsdatum:
26. April 2006 (online)

Abstract

A variety of unsymmetrical monosulfides can be synthesized in good yields by copper-catalyzed coupling of disulfides with organoboronic acids in air. Furthermore, this method can result in the successful aryl- or alkylation of both organosulfide groups in a disulfide.

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Typical Procedure. To a mixture of CuI (1.9 mg, 0.01 mmol), bpy (1.6 mg, 0.01 mmol), DMSO (0.2 mL), and H2O (0.1 mL) were added Ph2S2 (43.7 mg, 0.2 mmol) and PhB(OH)2 (73.1 mg, 0.60 mmol), and the mixture was stirred at 100 °C for 12 h in air. After evaporation of the solvent, the residue was dissolved in Et2O. The solution was washed with H2O, brine, and dried over anhyd MgSO4. Chromatography (silica gel; hexane) gave diphenyl sulfide (72.1 mg, 97%).
Diphenyl Sulfide: IR (neat): 3072, 1579, 1475, 1439 cm-1. 1H NMR (270 MHz, CDCl3): δ = 7.36-7.22 (m, 10 H).
13C NMR (67.5 MHz, CDCl3): δ = 135.7, 131.0, 129.1, 127.0. Anal. Calcd for C12H10S: C, 77.37; H, 5.41. Found: C, 77.18; H, 5.49.
4-Formylphenyl Phenyl Sulfide: IR (neat): 3058, 1697, 1591, 1561, 1475 cm-1. 1H NMR (270 MHz, CDCl3): δ = 9.89 (s, 1 H), 7.70 (d, J = 8.6 Hz, 2 H), 7.49-7.53 (m, 2 H), 7.43-7.39 (m, 3 H), 7.23 (d, J = 8.6 Hz, 2 H). 13C NMR (67.5 MHz, CDCl3): δ = 191.0, 147.1, 134.2, 133.6, 131.2, 130.0, 129.7, 129.0, 127.1. Anal. Calcd for C13H10OS: C, 72.87; H, 4.70. Found: C, 72.69; H, 4.95.
Cyclohexyl Phenyl Sulfide: IR (neat): 2929, 2852, 1583, 1479, 1448 cm-1. 1H NMR (270 MHz, CDCl3): δ = 7.40-7.36 (m, 2 H), 3.30-3.17 (m, 3 H), 3.13-3.05 (m, 1 H), 2.01-1.96 (m, 2 H), 1.78-1.74 (m, 2 H), 1.63-1.57 (m, 1 H), 1.42-1.25 (m, 5 H). 13C NMR (67.5 MHz, CDCl3): δ = 135.1, 131.8, 128.6, 126.5, 46.5, 33.3, 26.0, 25.7. Anal. Calcd for C12H16S: C, 74.94; H, 8.39. Found: C, 74.96; H, 8.35.

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A disulfide bond can be cleaved by CuI; see ref. 5b and 5d.

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4-Formylphenyl Phenyl Selenide: IR (neat): 3055, 2828, 2733, 1696, 1587 cm-1. 1H NMR (270 MHz, CDCl3): δ = 9.90 (s, 1 H), 7.67 (d, J = 8.6 Hz, 2 H), 7.62-7.59 (m, 2 H), 7.41-7.34 (m, 5 H). 13C NMR (67.5 MHz, CDCl3): δ = 191.2, 142.6, 135.4, 134.4, 130.1, 130.0, 129.7, 128.8, 127.8. Anal. Calcd for C13H10OSe: C, 59.78; H, 3.86. Found: C, 59.55; H, 3.96.
4-Formylphenyl Phenyl Telluride: IR (neat): 3052, 2827, 2734, 1694, 1582 cm-1. 1H NMR (270 MHz, CDCl3): δ = 9.89 (s, 1 H), 7.83 (d, J = 8.3 Hz, 2 H), 7.62-7.61 (m, 4 H), 7.59-7.25 (m, 3 H). 13C NMR (67.5 MHz, CDCl3): δ = 191.5, 139.8, 135.6, 135.1, 129.8, 128.9, 126.6, 112.9. Anal. Calcd for C13H10OTe: C, 50.40; H, 3.25. Found: C, 50.12; H, 3.35.