Synlett 2016; 27(01): 80-82
DOI: 10.1055/s-0034-1378827
letter
© Georg Thieme Verlag Stuttgart · New York

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

Philip C. Bulman Page*
a   School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, Norfolk NR4 7TJ, UK   Email: p.page@uea.ac.uk
,
Benjamin R. Buckley*
b   Chemistry Department, Loughborough University, Ashby Road, Loughborough, Leicestershire, LE11 3TU, UK
,
Claire Elliott
b   Chemistry Department, Loughborough University, Ashby Road, Loughborough, Leicestershire, LE11 3TU, UK
,
Yohan Chan
a   School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, Norfolk NR4 7TJ, UK   Email: p.page@uea.ac.uk
,
Nicolas Dreyfus
c   Lilly Research Centre, Erl Wood Manor, Sunninghill Road, Windlesham, Surrey, KT 13 8JT, UK
,
Frank Marken
d   Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK
› Author Affiliations
Further Information

Publication History

Received: 28 June 2015

Accepted after revision: 02 July 2015

Publication Date:
12 August 2015 (online)


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

Supporting Information

 
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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: νmax = 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: νmax = 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: νmax = 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: νmax = 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.