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

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.

unsymmetrical monosulfide - diaryl disulfide - organo­boronic acid - copper catalyst

References and Notes

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<A NAME="RU01506ST-11">11</A>

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.

<A NAME="RU01506ST-15">15</A>

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.