Preparation and Reactivity of Polystyrene-Supported Iodosylbenzene: Convenient Recyclable Oxidizing Reagent and Catalyst

Abstract

A facile preparation of novel polystyrene-supported iodosylbenzene (PS-ISB, loading of IO up to 1.50 mmol/g) from iodopolystyrene is described. This resin has been successfully used for efficient oxidation of a diverse collection of alcohols to aldehydes and ketones in the presence of BF₃˙OEt₂. PS-ISB can also be employed as efficient co-catalyst in combination with RuCl₃ in the catalytic oxidation of alcohols and aromatic hydrocarbons, respectively, to corresponding carboxylic acids and ketones using Oxone as the stoichiometric oxidant.

polymers - iodine - oxidation - iodosylbenzene - recyclable reagent

References and Notes

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8

Preparation of PS-ISB (2) PS-DIB (1,⁷ 1.430 g, 3.0 mmol) and NaOH (0.400 g, 10.0 mmol) were grinded intensively in a mortar at r.t. for 10 min. The resulting mixture was left to stay at r.t. for 2 h, then H₂O (15 mL) was added and stirred overnight, the mixture was filtered, washed with H₂O (3 × 3 mL), acetone (3 × 3 mL), and Et₂O (3 × 3 mL) subsequently, and then dried in vacuum to give a yellow powder (1.05 g). Elem. Anal. (%): O, 8.68; I, 37.19. IR (KBr): ν = 761 (I=O) cm^-¹.

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10

General Procedure for Oxidations Using PS-ISB (2)
To a vigorously stirred suspension of PS-ISB (2, 0.3 mmol) in CH₂Cl₂ (2 mL), BF₃˙OEt₂ (0.040 mL) was added, and the resulting mixture was stirred at r.t. for 15 min. To the mixture, the appropriate alcohol (0.2 mmol) or Ph₃P (0.2 mmol) or anthracene (0.1 mmol) was added. The resulting mixture was stirred at r.t. for the indicated time (Table  [¹] ). A portion of the crude reaction mixture (100 µL) was poured into a flask with Et₂O (0.5 mL) to precipitate PS-IB, then the mixture was passed through a 2-3 cm of silica gel suspended in a Pasteur pipette, and the resulting solution was analyzed by GC-MS to determine the conversion of organic substrates.

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13

Typical Procedure of the PS-ISB/RuCl ₃ -Cocatalyzed Oxidation of Alcohols Oxone (0.92 g, 1.5 mmol) was added to a mixture of 1-phenylethanol (122 mg, 1 mmol, Table  [²] , entry 7), PS-ISB (2, 0.070 g, 0.1 mmol, 10 mol%), and RuCl₃ (10 µL of 0.20 M solution in H₂O, 0.002 mmol, 0.2 mol%) in MeCN (3 mL) and H₂O (3 mL) in one portions under stirring at r.t. (the reaction was monitored by TLC by the disappearance of 1-phenylethanol). Then EtOAc (15 mL) and H₂O (20 mL) were added, and the mixture was stirred for 5 min. The polymeric catalyst (PS-ISB) was filtered, washed with H₂O (2 × 2 mL) and EtOAc (2 × 2 mL), and collected for next run. The organic solution was separated, and the aqueous phase and extracted with EtOAc (2 × 15 mL). The organic solutions were combined, washed with NaCl (sat. solution, 20 mL), and dried over anhyd Na₂SO₄. Removal of the solvent under vacuum afforded acetophenone (114 mg, 95%). The oxidation of other alcohols and hydrocarbons (Table  [²] ) was performed by using a similar procedure.