Preparation and Reactivity of Polystyrene-Supported Iodosylbenzene Sulfate: An Efficient Recyclable Oxidizing System

Abstract

A new polymer-supported hypervalent iodine reagent, polystyrene-supported iodosylbenzene sulfate (PS-IBS), can be conveniently prepared by the reaction of polystyrene-supported (diacetoxyiodo)benzene (PS-DIB) with sodium bisulfate monohydrate under solvent-free conditions. This new recyclable reagent effects clean and efficient oxidation of a wide range of alcohols and sulfides to the corresponding carbonyl compounds or sulfoxides in high conversions under mild conditions. The final products are conveniently separated from the polymeric byproduct by simple filtration and isolated in good purity after evaporation of solvent. Recycling of the resin is possible with minimal loss of activity after several reoxidations.

Key words

polymers - iodine - oxidation - iodosylbenzene(III) sulfate - recyclable reagent

References and Notes

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7

Structure 3 is assigned for polystyrene-supported iodosyl-benzene sulfate based on X-ray single crystal data for the monomeric analogue 1, which has been prepared using a similar solid-state procedure. We realize that the presence of the polystyrene chain may have a significant effect on the actual structure of the iodosylbenzene sulfate moiety. The ESI-MS study of compound 1 in aq solution indicates the presence of hydroxy(phenyl)iodonium ion, [PhI(OH)]⁺ and hydrated iodosylbenzene, PhI(OH)₂.^4a,b It is possible that similar polymer-bound iodine(III) moieties are present the structure of resin 3.

9

Preparation of PS-IBS (3)
PS-DIB (2)⁸ (1.430 g, 3.0 mmol) and NaHSO₄˙H₂O (0.414 g, 3.0 mmol) were grinded intensively in a mortar at r.t. for 10 min. The resulting mixture was left to stay at r.t. overnight, then 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 (1.45 g). Elemental analysis: S, 2.18% (loading of S: 0.68 mmol/g). IR (KBr): ν = 3406, 2923, 1628, 1481, 1406, 1118, 1004, 819, 766, 619 cm^-¹.

10

General Procedure for Oxidations Using PS-IBS
To a solution of sulfide 6 (0.2 mmol) or alcohol 5 (0.2 mmol) in aq MeCN (2 mL of MeCN-H₂O, 5:1) was added PS-IBS 3 (206 mg, 0.140 mmol) and KBr (2.4 mg, 0.02 mmol) at r.t., and the mixture was magnetically stirred until the sulfide or alcohol was consumed (monitored by TLC). The mixture was filtered, and the resin was washed with EtOAc (3 × 1 mL). The filtrate was washed with sat. NaHCO₃ (3 mL) [for alcohols, the filtrate may be washed with 5% H₂SO₄ (3 mL) before this operation], then extracted with EtOAc (3 × 2 mL). The combined organic solution was washed with brine (3 mL), water (3 mL), and dried over Na₂SO₄. The solvent was evaporated to yield respective products 7-9; the products were identified by comparison of their MS and NMR spectra with commercially available samples.