Magnetically Recoverable Osmium Catalysts with Osmium–Diolate Esters for Dihydroxylation of Olefins

 

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Abstract

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.