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Synlett 2005(1): 149-151  
DOI: 10.1055/s-2004-836052
LETTER
© Georg Thieme Verlag Stuttgart · New York

Sulfamide Synthesis via Pd-Catalysed Cross-Coupling

Kilian Muñiz*, Martin Nieger
Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany
Fax: +49(228)735813; e-Mail: kilian.muniz@uni-bonn.de;
Further Information

Publication History

Received 16 July 2004
Publication Date:
29 November 2004 (online)

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Abstract

A novel efficient procedure for the improved synthesis of aryl-substituted sulfamides via a Pd-catalysed arylation of sulf­amide is reported.

Key words

amines - amides - sulfur compounds - catalysis - palladium

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X-Ray Analysis. E-mail: m.nieger@joyx.joensuu.fi.

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Typical Synthetic Procedure for Amination of Halo-arenes via Pd-Coupling: A solution of compound 1 (3.3 mmol) and bromo benzene 2 (1.0 mmol) in freshly distilled toluene are treated with dipalladium(0)-dba complex (0.075 mmol), tris(tert-butyl)phosphine (0.2 mmol) and caesium carbonate (1 mmol) and heated to 50 °C overnight. The reaction mixture is cooled to r.t., filtered over celite and evaporated under reduced pressure. The pure product was usually obtained by crystallization from methanol.
Analytical data for compound 3: 1H NMR (DMSO-d 6): δ = 4.05 (d, J = 1.2 Hz, 2 H, CH 2), 6.55 (br s, 2 H, NH 2), 6.92 (t, J = 1.2 Hz, 1 H, NH), 7.11-7.40 (m, 5 H, arom.). 13C NMR (DMSO-d 6): δ = 46.5 (CH2), 127.3, 128.1, 128.5 (arom. CH), 139.0 (C ipso). Anal. Calcd for C7H10N2O2S: C, 45.15; H, 5.41; N, 15.04; S, 17.22. Found: C, 45.29; H, 5.09; N, 14.81; S, 17.50.

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Typical Procedure for DMAP-Mediated Synthesis of Sulfamides: A solution of sulfamoyl chloride (5 mmol) in CH2Cl2 (10 mL) is treated with an additional amount of dry toluene (10 mL) and stirred at 0 °C. To this solution, DMAP (1.0 mmol) is added in one portion followed by addition of Et3N (5.5 mmol) and the respective aniline (1.0 mmol). The resulting yellow solution is stirred first at 0 °C, then at r.t. for 5 h. The solvents are removed to a remaining volume of approx. 4 mL and extracted with boiling water. Evaporation of the aqueous phase yields the respective sulfamides. Alternatively, some of the products can be distilled directly from the crude reaction mixture.

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Data on the X-Ray Analysis of Compound 3. Crystallographic data (excluding structure factors) for the structure reported have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-241627. Copies of the data can be obtained free of charge on application to the CCDC, 12 Union Road, Cambridge CB2 1EZ UK (fax: +44(1223)336033; email: deposit@ccdc.cam.ac.uk).