Sulfamide Synthesis via Pd-Catalysed Cross-Coupling

Abstract

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

amines - amides - sulfur compounds - catalysis - palladium

References

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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.

<A NAME="RG27204ST-12">12</A>For a related procedure of Hartwig-Buchwald coupling employing sulfoximines, see:

<A NAME="RG27204ST-12">12</A> Bolm C. Hildebrand JP.
J. Org. Chem.  2000,  65:  169 

<A NAME="RG27204ST-13">13</A> While this work was under reviewing, a related cross-coupling was reported independently: Alcaraz L. Bennion C. Morris J. Meghani P. Thom SM. Org. Lett.  2004,  6:  2705 

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<A NAME="RG27204ST-15">15</A> For a related procedure employing DMA or NMP, see: Okada M. Iwashita S. Koizumi N. Tetrahedron Lett.  2000,  41:  7047 

<A NAME="RG27204ST-16">16</A>

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.

<A NAME="RG27204ST-17">17</A>

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: [phone]; email: [e-mail]).