Osmium on Chelate Resin: Nonvolatile Catalyst for the Synthesis of Diols from Alkenes

 

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Abstract

Osmium tetraoxide (OsO₄) was immobilized on a commercially available chelate resin DIAION CR11 (CR11) just by simply immersing it in a methanol solution of OsO₄ at room temperature. The resulting purple solid, 5% Os/CR11, indicated no volatility, and effectively catalyzed the oxidation of various alkenes to the corresponding diols.

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• 23 Preparation of 5% Os/CR11 To a solution of OsO₄ (1.00 g, 3.93 mmol) in MeOH (600 mL) was added DIAION CR11 (40.3 g, H₂O ca. 60–65%), and the mixture was stirred at r.t. under an Ar atmosphere for 3 d. The resulting purple resin was collected on a filter paper, washed with MeOH (3 × 100 mL), then dried under reduced pressure to give 5% Os/CR11 (16.3 g). The filtrate and MeOH wash were diluted to 1 L with MeOH in a volumetric flask. The inductively coupled plasma atomic emission spectrometry (ICP-AES) of the combined filtrate and MeOH wash detected 1 mg/L of osmium species (1 mg Os in 1 L MeOH), indicating that 746.6 mg Os was embedded on the CR11 [3.93 mmol × 190.23 (molecular weight of Os) – 1 mg (Os in MeOH)]. Therefore, the amount of Os on CR11 was determined to be ca. 5 weight% osmium [746.6 (mg, weight of Os) ÷ 16300 (mg, weight of catalyst) × 100 = 4.6%].
• 24 The immobilization manner of osmium to CR11 was not characterized
• 25 Water should be necessary for the hydrolysis of the intermediary osmate ester, which is supposedly obtained by the cycloaddition reaction of osmium species with an alkene.
• 26 General Procedure for the 5% Os/CR11-Catalyzed Oxidation of Alkenes in 70% Aqueous Acetone A mixture of the alkene (250 μmol), NMO (32.2 mg, 275 μmol), and 5% Os/CR11 (9.5 mg, 2.50 μmol) in 70% aq acetone (500 μL) was stirred under an Ar atmosphere at r.t. After the consumption of the alkene (TLC analysis), the 5% Os/CR11 was removed by filtration, and the filtrate was concentrated in vacuo. The residue was passed through a short silica gel column chromatography to give the corresponding diol. The NMR data of the products were identical to those in the literature, see the Supporting Information.
• 27 General Procedure for the 5% Os/CR11-Catalyzed Oxidation of Alkenes in t-BuOH A mixture of the alkene (250 μmol), NMO (43.9 mg, 375 μmol), 5% Os/CR11 (47.6 mg, 12.5 μmol), and H₂O (9.0 μL, 500 μmol) in t-BuOH (500 μL) was stirred under an Ar atmosphere at r.t. After 24 h, the 5% Os/CR11 was removed by filtration, and the filtrate was concentrated in vacuo. The residue was passed through a short silica gel column chromatography to give the corresponding diol.
• 28 It is not clear why satisfactory reuse of 5% Os/CR11 was not achieved even under conditions B where only a small amount of osmium was leached out from the catalyst, although the decrease of each run in the catalyst activity was lower than that under conditions A.

• Supplementary Material