Transition-Metal-Free, Chemoselective Aerobic Oxidations of Sulfides and Alcohols with Potassium Nitrate and Pyridinium Tribromide or Bromine

Abstract

An efficient oxidation of sulfides with air catalyzed by the combination of potassium nitrate with pyridinium tribromide under transition-metal-free conditions was reported. By replacing pyridinium tribromide with bromine, the reaction system was also useful in the oxidation of alcohols. All reactions afforded the corresponding products in good to excellent yields with high chemoselectivities.

aerobic oxidation - sulfide - alcohol - chemoselectivity - transition-metal-free

References and Notes

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13

General Methods
^¹H NMR and ^¹³C NMR spectra were obtained with a Bruker AVANCE 600 spectrometer in CDCl₃ with TMS as an internal standard. Infrared spectra were recorded with a Bruker Tensor 27 FT-IR spectrometer using KBr pellets. GC-MS was performed on a FINNIGAN Trace DSQ chromatograph.
Procedure for Oxidation of Sulfide Using KNO ₃ -PyHBr ₃ /Br ₂ as Catalyst A typical experiment was carried out in an open reaction tube. Sulfide (1 mmol) was added to the mixture of KNO₃ (0.1 mmol) and PyHBr₃ (or bromine; 0.15 mmol) in MeCN (2 mL). The reaction mixture was stirred under aerial conditions at r.t. The reaction progress was detected by
GC and TLC. After the starting material had disappeared, Na₂S₂O₃ aq solution was used to quench the reaction. CH₂Cl₂ was added to the reaction mixture, and the two phases were separated. The aqueous layer was extracted with CH₂Cl₂. The combined organic layers were washed with H₂O and dried over MgSO₄. The solvent was removed under vacuum, and the residue was purified by chromatography. Representative Spectral Data of Sulfoxide - Methyl Phenyl Sulfoxide IR (KBr): ν_max = 3265, 1477, 1038, 749, 692 cm^-¹. ^¹H NMR (600 MHz, CDCl₃): δ = 2.73 (s, 3 H), 7.48-7.54 (m, 3 H), 7.64-7.65 (d, 2 H, J = 7.44 Hz). ^¹³C NMR (150 MHz, CDCl₃): δ = 44.13, 123.6, 129.5, 131.2, 145.7. MS (EI, 70 eV): m/z (%) = 140 [M⁺].^³h Procedure for Oxidation of Benzaldehydes and Acetophenones Using KNO ₃ -Br ₂ /PyHBr ₃ as Catalyst A typical experiment was carried out in an open reaction tube. Benzaldehyde or acetophenone (1 mmol) was added to the mixture of KNO₃ (0.2 mmol) and bromine (0.3 mmol) in MeCN (2 mL). The reaction mixture was stirred under aerial conditions at 50 ˚C. The reaction progress was detected by GC and TLC. After the starting material had disappeared, Na₂S₂O₃ aq solution was used to quench the reaction. CH₂Cl₂ was added to the reaction mixture, and the two phases were separated. The aqueous layer was extracted with CH₂Cl₂. The combined organic layers were washed with H₂O and dried over MgSO₄. The solvent was removed under vacuum, and the residue was purified by chromatography.
Representative Spectral Data of Aldehyde - Benzaldehyde
IR (KBr): ν_max = 3064, 2819, 1701, 1311, 1203, 746 cm^-¹. ^¹H NMR (600 MHz, CDCl₃): δ = 7.51-7.54 (t, 2 H, J = 7.54 Hz), 7.61-7.64 (t, 1 H, J = 7.43 Hz), 7.87-7.88 (d, 2 H, J = 7.69 Hz), 10.00 (s, 1 H). ^¹³C NMR (150 MHz, CDCl₃): δ = 129.0, 129.7, 134.4, 136.4, 192.4. MS (EI, 70 eV): m/z (%) = 106 [M⁺].^²c