Chemoselective Oxidation of Sulfides to Sulfoxides with Urea–Hydrogen Peroxide Complex Catalysed by Diselenide

Dedicated to Prof Steven Victor Ley for the occasion of his 70^th birthday.

Abstract

A highly selective catalytic oxidation system has been developed for the conversion of sulfides into the corresponding sulfoxides using urea–hydrogen peroxide as stoichiometric oxidant in the presence of a catalytic quantity of diphenyl diselenide.

Key words

sulfoxidation - urea–hydrogen peroxide - diphenyl diselenide - oxidation - catalysis

• References and Notes

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• 24 General Procedure for the Oxidation of Sulfides Using Urea–Hydrogen Peroxide and Diphenyl Diselenide UHP (2 mmol) was dissolved in CH₂Cl₂ (2 mL), and the solution was stirred at r.t. A solution of Ph₂Se₂ (1 mol%) and sulfide (2 mmol) in CH₂Cl₂ (2 mL) was added to the UHP solution. The mixture was stirred at r.t. for 24 h or until complete conversion to sulfoxide was observed by TLC. Extraction was carried out with CH₂Cl₂ (3 × 5 mL), after the addition of H₂O (5 mL), and the combined organic solutions were washed with brine (50 mL), dried (MgSO₄), filtered, and the solvents removed under reduced pressure. Sulfoxide products were purified where necessary by column chromatography. Sulfoxide from Thiochroman-4-one Yellow oil. FTIR: ν_max = 1694, 1585, 1325, 1282, 1237, 1182, 1120, 1080, 1039, 854 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.86–2.97 (1 H, m), 3.43–3.56 (3 H, m), 7.65–7.68 (1 H, m), 7.75–7.79 (1 H, m), 7.87 (1 H, dd, J = 8.1, 7.6 Hz), 8.14 (1 H, dd, J = 8.0, 7.6 Hz) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 30.3, 46.6, 128.5, 128.9, 132.1, 134.6, 145.5, 192.1 ppm. Sulfoxide from 4-Fluorothioanisole Yellow oil. FTIR: ν_max = 3096, 3062, 2996, 1655, 1641, 1046 (S=O), 958, 834 (C–F) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.73 (3 H, s), 7.21–7.26 (2 H, m), 7.66–7.69 (2 H, m) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 44.0, 117.0, 125.5, 130.1, 141.2 ppm. Sulfoxide from 2-Chloroethyl Ethyl Sulfide Yellow oil. FTIR: ν_max = 1653, 1455, 1301, 1127, 1020, 864 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.37 (3 H, t, J = 7.6 Hz), 2.76–2.86 (2 H, m), 3.04–3.08 (2 H, m), 3.89–4.00 (2 H, m) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 6.7, 37.0, 46.0, 54.0 ppm. Sulfoxide from Furfuryl Methyl Sulfide Yellow oil. FTIR: ν_max = 2972, 2916, 1423, 1033, 933, 744 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.52 (3 H, s), 4.06 (2 H, q, J = 13.92 Hz), 6.40 (2 H, m), 7.39 (1 H, dd, J = 2.0 Hz) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 37.9, 52.2, 111.2, 143.5, 143.9 ppm.