Oxidation of Amines and Sulfides Catalyzed by an Assembled Complex of Phosphotungstate and Non-Cross-Linked Amphiphilic Polymer

Abstract

Oxidation of sulfides and amines was performed with an assembled catalyst of phosphotungstate and non-cross-linked amphiphilic polymer. The reactions proceeded with hydrogen peroxide under organic solvent-free conditions. This insoluble catalyst was reused five times with the turnover number up to 500.

polymers - tungsten - oxidation - amines - sulfides

References

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General Procedure for the oxidation of amines catalyzed by catalyst 1: To a suspension of 1 [5a] (40 mg; 5 mmol) and 2 (2.52 mmol) was added 2.5% H₂O₂ aqueous solution (7.56 mmol) dropwise for 50 min at 0 °C (entry 3: added dropwise at r.t.; entry 5: added one portion at r.t.). The mixture was stirred at room temperature (entry 5: 40 °C; entry 7: 0 °C) for 3-24 h, before it was diluted with EtOAc and filtered through a glass filter. Brine was added to the filtrate, and it was extracted with EtOAc (× 3). The extract was washed with brine, dried over Na₂SO₄, filtered, dried in vacuo, and purified by column chromatography to give 3.

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The reaction of 2c was performed in CH₂Cl₂ (0.25 M) at room temperature for 95 h, providing 3c and 3c′ in 95% yield (3c/3c′ = 1.76:1). Even in the reaction of 3c or 3c′ with CH₂Cl₂, isomerizations were hardly observed.

<A NAME="RU08702ST-10">10</A>

General procedure for the oxidation of sulfides to sulfones catalyzed by catalyst 1: The mixture of 1, 4 and 35-40% H₂O₂ aqueous solution was shaken by PetiSyther ^® (Shimadzu Scientific Research Inc. Japan) at 700 rpm at 50 °C for 4-7 h, it was diluted with EtOAc and filtered. To the filtrate was added saturated Na₂S₂O₃ and brine, and it was extracted with EtOAc (× 3), dried over Na₂SO₄, filtered, dried in vacuo, and purified by column chromatography to give the products. While the shaker (PetiSyther ^®) for solid-phase syntheses was used in these reactions, the glassware vessel equipped with a magnetic stirrer can be also used.

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The reaction with 2.5% H₂O₂ proceeded slower (55 h) than that with 35-40% H₂O₂, providing sulfone 6a in 95% yield.

<A NAME="RU08702ST-13">13</A>

Noyori et al. reported that the oxidation of sulfides to sulfoxides proceeded efficiently in hydrogen peroxide without catalysts, so that we have not examined the selective oxidation to sulfoxide. See ref. [11h]

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<A NAME="RU08702ST-18B">18b</A>

On the other hand, Ishii et al. proved that [π-C₅H₅N⁺(CH₂)₁₅CH₃]₃PW₁₂O₄₀ ^3- maintained the structure closed to Keggin unit after treatment with hydrogen peroxide. See ref. [11b]