Magnetically Recoverable Osmium Catalysts with Osmium–Diolate Esters for Dihydroxylation of Olefins
Received: 26 February 2013
Accepted after revision: 18 March 2013
11 April 2013 (eFirst)
We prepared magnetically recoverable osmium catalysts with stable osmium–diolate esters and applied them to the dihydroxylation of olefins. By employing 2 mol% of the magnetic osmium catalyst, the dihydroxylation reaction proceeded smoothly to provide the corresponding vicinal diol with a low level of osmium leaching. After completion of the dihydroxylation, the osmium catalyst was readily recovered by use of an external magnet and was recycled up to five times.
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- 9 General Procedure To a t-BuOH–CH2Cl2 (2:1, v/v) solution (3 mL) of the olefin (1 mmol) was successively added a magnetic osmium catalyst (0.02 mmol), NMO (1.3 mmol), and H2O (2.6 or 11 mmol) at r.t. under an argon atmosphere. After stirring of the resulting mixture, the dihydroxylation reaction was completed (monitored by TLC). A magnetic osmium catalyst was separated by magnetic decantation using an external magnet followed by washing with t-BuOH–CH2Cl2, and the recovered magnetic osmium catalyst was reused for subsequent dihydroxylation reactions.
- 10 Compound 7a: olefin moiety 0.19 mmol/g, C18H37 group 0.41 mmol/g; compound 7b: olefin moiety 0.16 mmol/g, CH2CH2C8F17 group 0.44 mmol/g.
- 11 Preparation of 8a OsO4 was prepared in situ by stirring a CH2Cl2–Η2Ο (5:1, v/v) solution (90 mL) of K2OsO4·2H2O (111 mg, 0.3 mmol) and NMO (703 mmol, 6 mmol) overnight at r.t. under an argon atmosphere. To the resulting solution, 7a (1.67 g, 0.316 mmol) and t-BuOH (150 mL) were added, and the mixture was vigorously stirred for 7 h at r.t. under an argon atmosphere. The obtained magnetic nanoparticles were separated by magnetic decantation using an external magnet and washed five times with t-BuOH–CH2Cl2. After drying under reduced pressure, 1.67 g of 8a was obtained as a black powder.
- 12 Selected Data for Compound 8a Black powder. IR (KBr) 2922, 2853, 1655, 1638, 1047, 1015, 993, 571 cm–1. Anal. Found: C, 11.21; H, 1.89; N, 0.45; Os, 2.63.