An Efficient Palladium-Catalyzed Synthesis of Unsymmetrical Diaryl Sulfones from Aryl Bromides/Triflates and Arenesulfinates

Abstract

The palladium-catalyzed coupling of arenesulfinate salts and aryl bromides or triflates provides a simple and extremely efficient route to unsymmetrical diaryl sulfones. The reaction was found to be strongly influenced by the presence of n-Bu₄NCl. The ammonium salt tends to favor the formation of sulfones with neutral, electron-rich and slightly electron-poor aryl bromides or trif­lates and to hamper the reaction with electron-poor aryl bromides or triflates.

Key words

coupling - sulfones - palladium - catalysis - arenesul­finates

References

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  Rutherford, J. F.; Rainka, M. P.; Buchwald, S. L. J. Am. Chem. Soc., article as soon as possible.

9

Cacchi, S.; Fabrizi, G.; Goggiamani, A.; Parisi, L. M. Org. Lett., in press.

18

Typical Procedure for the Preparation of Unsymmetrical Diaryl Sulfones with Electron-Poor Aryl Bromides or Triflates (Procedure B) (Table 2, Entry 28): In a Carousel Tube Reaction (Radley Discovery), to a solution of sodium p-toluenesulfinate (0.075 g, 0.420 mmol) and p-nitrophenyl bromide (0.0707 g, 0.350 mmol) in 2.0 mL of toluene under argon, Pd₂(dba)₃ (0.008 g, 0.009 mmol), Xantphos (0.010 g, 0.018 mmol) and Cs₂CO₃ (0.171 g, 0.525 mmol) were added. The mixture was warmed at 120 °C under stirring for 5 h. After cooling, the reaction mixture was diluted with ethyl acetate, washed with water, dried over Na₂SO₄ and concentrated under reduced pressure. The reaction mixture was purified by chromatography (silica gel, 35 g; n-hexane/ethyl acetate 80/20 v/v) to give 0.076 g of p-nitrophenyl p-tolyl sulfone (78% yield): Mp 164-165 °C. IR (KBr): 2926, 1351, 1157 cm^-1. ¹H NMR (CDCl₃): δ = 8.31 (d, J = 8.9 Hz, 2 H), 8.10 (d, J = 8.9 Hz, 2 H), 7.84 (d, J = 8.4 Hz, 2 H), 7.34 (d, J = 8.1 Hz, 2 H), 2.41 (s, 3 H). ¹³C NMR (CDCl₃): δ = 150.3, 147.9, 145.5, 137.1, 130.4, 128.9, 128.2, 124.5, 21.7. Anal Calcd for C₁₃H₁₁O₄S: C, 56.31; H, 4.00. Found: C, 56.23; H, 3.99.
With neutral, electron-rich and slightly electron-poor aryl bromides or triflates, 1.2 equiv of n-Bu₄NCl were added (procedure A).