Transition-Metal-Free, Chemoselective Aerobic Oxidations of Sulfides and Alcohols with Potassium Nitrate and Pyridinium Tribromide or Bromine
27 January 2011 (online)
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
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References and Notes
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): νmax = 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): νmax = 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