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

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.

Key words

chelate resin - diols - osmium - oxidation - supported catalyst

• References and Notes

• 1a Schröder M. Chem. Rev. 1980; 80: 187
• 1b Kolb HC, Van Nieuwenhze MS, Sharpless KB. Chem. Rev. 1994; 94: 2483
• 2a Nagayama S, Endo M, Kobayashi S. J. Org. Chem. 1998; 63: 6094
• 2b Wako Pure Chemical Industries, Ltd., Code No. 153-02081.
• 3a Kobayashi S, Ishida T, Akiyama R. Org. Lett. 2001; 3: 2649
• 3b Akiyama R, Matsuki N, Nomura H, Yoshida H, Yoshida T, Kobayashi S. RSC Adv. 2012; 2: 7456
• 3c Wako Pure Chemical Industries, Ltd., Code No. 158-02411.
• 4 Kobayashi S, Endo M, Nagayama S. J. Am. Chem. Soc. 1999; 121: 11229
• 5a Choudary BM, Chowdari NS, Jyothi K, Kantam ML. J. Am. Chem. Soc. 2002; 124: 5341
• 5b Choudary BM, Jyothi K, Madhi S, Kantam ML. Adv. Synth. Catal. 2003; 345: 1190
• 6 Jun B.-H, Kim J.-H, Park J, Kang H, Lee S.-H, Lee Y.-S. Synlett 2008; 2313
• 7 Lohray BB, Thomas A, Chittari P, Ahuja JR, Dhal PK. Tetrahedron Lett. 1992; 37: 5453
• 8 Choudary BM, Roy M, Roy S, Jyothi K, Kantam ML, Sreedhar B, Kumar KV. Adv. Synth. Catal. 2006; 348: 1734
• 9 Reddy SM, Srivasulu M, Reddy YV, Narasimhulu M, Venkateswarlu Y. Tetrahedron Lett. 2006; 47: 5285
• 10 Lee BS, Mahajan S, Janda KD. Tetrahedron Lett. 2005; 46: 4491
• 11 Declue MS, Siegel JS. Org. Biomol. Chem. 2004; 2: 2287
• 12 Pini D, Petri A, Nardi A, Rosini C, Salvadori P. Tetrahedron Lett. 1991; 32: 5175
• 13 Yang JW, Han H, Roh HH, Lee S.-g, Song CE. Org. Lett. 2002; 4: 4685
• 14 Fujita K, Inoue K, Tsuchimoto T, Yasuda H. Chem. Pharm. Bull. 2012; 60: 1594
• 15a Severeyns A, De Vos DE, Fiermans L, Verpoort F, Grobet PJ, Jacobs PA. Angew. Chem. Int. Ed. 2001; 40: 586
• 15b Choudary BM, Chowdari NS, Jyothi K, Kumar NS, Kantam ML. Chem. Commun. 2002; 586
• 15c Caps V, Paraskevas I, Tsang SC. Appl. Catal., A 2003; 252: 37
• 15d Moen AR, Ruud K, Anthonsen T. J. Mol. Catal. B: Enzym. 2008; 50: 74
• 16 Metin Ö, Alp NA, Akbayrak S, Biçer A, Gültekin MS, Özkar S, Bozkaya U. Green Chem. 2012; 14: 1488
• 17 Motorina I, Crudden CM. Org. Lett. 2001; 3: 2325
• 18a Choudary BM, Chowdari NS, Madhi S, Kantam ML. Angew. Chem. Int. Ed. 2001; 40: 4620
• 18b Choudary BM, Chowdari NS, Kantam M, Raghavan KV. J. Am. Chem. Soc. 2001; 123: 9220
• 18c Choudary BM, Chowdari NS, Madhi S, Kantam ML. J. Org. Chem. 2003; 68: 1736
• 19a Choudary BM, Jyothi K, Kantam ML, Sreedhar B. Adv. Synth. Catal. 2004; 346: 45
• 19b Choudary BM, Jyothi K, Roy M, Kantam ML, Sreedhar B. Adv. Synth. Catal. 2004; 346: 1471
• 20a Koivula R, Lehto J, Pajo L, Gale T, Leinonen H. Hydrometallurgy 2000; 56: 93
• 20b Cavaco A, Fernandes S, Quina MM, Ferreira LM. J. Hazard. Mater. 2007; 144: 634
• 20c Cavaco SA, Fernandes S, Augusto CM, Quina MJ, Gando-Ferreira LM. J. Hazard. Mater. 2009; 169: 516
• 20d Gando-Ferreira LM, Romao IS, Quina MJ. Chem. Eng. J. 2011; 172: 277
• 21 Homepage for DIAION of Mitsubishi Chemical Co., see http://www.diaion.com/en/.
• 22 Monguchi Y, Nozaki K, Maejima T, Shimoda Y, Sawama Y, Kitamura Y, Kitade Y, Sajiki H. Green Chem. 2013; 15: 490
• 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.