Oxidative Cleavage of C=C Bonds with Singlet Molecular Oxygen Generated from Monoacetylated Bishydroperoxides

Abstract

The oxidative cleavage of C=C bonds adjacent to aryl and alkyl moieties was efficiently achieved with monoacetylated bishydroperoxides. The main active oxidant used in this reaction was singlet molecular oxygen, which was generated in situ from the base-mediated fragmentation of monoacetylated bishydroper­oxides. All the reactions proceeded smoothly at room temperature to furnish the respective carbonyl compounds in good yields within short reaction times.

Key words

peroxides - alkene - singlet molecular oxygen - oxidation - carbonyl compounds

• References and Notes

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• 48 Caution: Although we did not encounter any problem with trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane, it is potentially explosive and should be handled with precautions. All reactions should be carried out behind a safety shield inside a fume hood and transition-metal salts or heating should be avoided. Chemicals were purchased from Merck and were used without further purification. The dihydroperoxids used in the reactions were prepared according to the previously reported procedure (see refs. 46 and 47). Monoacetylation of these dihydroperoxides was carried out as described below. ¹H and ¹³C NMR spectra were obtained with a Bruker 200 MHz Avance spectrometer with CDCl₃ as solvent. FTIR spectra were recorded with a Bruker 500 scientific spectrometer in KBr pellets. Preparation of Bishydroperoxides; General Procedure: To a mixture of carbonyl compound (1 mmol) and silica sulfuric acid (SSA; 100 mg) in MeCN (4 mL) was added 30% aq H₂O₂ (3 mL), and the mixture was stirred at room temperature for the appropriate time. After completion of the reaction as monitored by thin-layer chromatography (TLC), the resulting mixture was filtered and washed with EtOAc (2 × 5 mL) to separate the solid catalyst. The combined filtrate was diluted with H₂O (5 mL) and extracted with EtOAc (3 × 5 mL). The combined organic layer was dried over anhydrous MgSO₄ and evaporated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane–EtOAc) to afford pure bishydroperoxides. The products were characterized on the basis of their physical properties and spectral (¹H, ¹³C NMR and IR) data, which were in accord with those reported. Monoacetylation of Bishydroperoxides; General Procedure: To a solution of bishydroperoxy compound (2.4 mmol) in CH₂Cl₂ (10 mL), was added 4-dimethylamino-pyridine (0.03 g, 0.25 mmol) and pyridine (0.2 g, 2.5 mmol). The reaction mixture was cooled to 0 °C and a solution of Ac₂O (0.25 g, 2.4 mmol) in CH₂Cl₂ (5 mL) was added dropwise during 5 min. Following completion of the addition, the reaction mixture was stirred for 30 min at 0 °C, and then diluted with CH₂Cl₂ (30 mL). The resulting mixture was treated with saturated NaHCO₃ (4 mL), H₂O (10 mL), brine (8 mL), and dried over anhydrous Na₂SO₄. Finally, evaporation of the solvent under reduced pressure gave a solid residue that was purified by silica gel flash chromatography (n-hexane–EtOAc, 10:1), to give the respective monoacetylated products as white solids. Characteristic Data of Oxidants A and B:
  Oxidant A: Yield: 84% (0.42 g); mp 38–40 °C; ¹H NMR (200 MHz, CDCl₃): δ = 9.43 (br s, 1 H, OOH), 2.67 (s, 2 H, 4-CH ₂), 2.17 (s, 3 H, Ac), 1.61 (s, 3 H, CH₃), 1.59 (s, 3 H, CH₃). ¹³C NMR (50 MHz, D₂O): δ = 171.7 (CO), 112.7 (C), 120.9 (C), 50.7, 17.6, 16.5. IR (KBr): 3389, 2869, 1750, 1433, 1380, 1333, 1173, 848, 790 cm^–1. Anal. Calcd for C₇H₁₂O₇: C, 40.38; H, 5.77. Found: C, 40.46; H, 5.72. Oxidant B: Yield: 80% (0.47 g); mp 35–37 °C; ¹H NMR (200 MHz, CDCl₃): δ = 10.22 (s, 1 H, OOH), 2.17 (s, 3 H, Ac), 2.00 (m, 4 H, CH₂), 1.76 (m, 4 H, CH₂), 1.57 (m, 1 H, CH), 0.88 (s, 9 H, CH₃). ¹³C NMR (50 MHz, D₂O): δ = 172.6 (CO), 120.9 (C-1), 47.3, 34.6, 34.5, 31.6, 27.3, 17.6. IR (KBr): 3240, 2869, 1750, 1365, 1186, 1070, 960 cm^–1. Anal. Calcd for C₁₂H₂₂O₅: C, 58.53; H, 8.94. Found: C, 58.62; H, 8.85. Oxidative Cleavage of Alkenes to the Respective Carbonyl Compounds; Typical Procedure: To a mixture of aryl alkene (1 mmol) and monoacetylated bishydroperoxide A or B (1 mmol) in MeCN (5 mL) was added 1.0 M aq n-Bu₄NF (2 mL). The mixture was stirred at room temperature for an appropriate time (Table 3). After completion of the reaction as monitored by TLC, the remaining peroxide was neutralized by the addition of aq Na₂SO₃. The resulting mixture was diluted with Et₂O (15 mL) and washed with H₂O (10 mL), then the organic layer was dried over anhydrous MgSO₄, filtered, and evaporated under reduced pressure. Purification of the crude solid residue by column chromatography gave the pure products. All the products produced from these reactions are known compounds and were characterized on the basis of their physical and spectral (IR, ¹H and ¹³C NMR) data, which were in accord with those reported.
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