Palladium-Catalyzed Aromatic Sulfonylation: A New Catalytic Domino Process Exploiting in situ Generated Sulfinate Anions

Abstract

Allylic sulfones are excellent precursors of aryl sulfones via a new Pd-catalyzed domino sequence involving in situ generation of sulfinate anions and subsequent cross-coupling with aryl ­iodides or bromides.

sulfones - sulfinate anions - catalysis - palladium - domino reaction

References and Notes

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11

Competitive deprotonation at the benzyl site might account for the failure of this coupling.

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13

Representative Experimental Procedure for the Domino Palladium-Catalyzed Generation-Arylation of Sulfinate Anions
To a solution of tris(dibenzylideneacetone)dipalladium (2 mol%) in toluene (500 µL) was added Xantphos ligand (5 mol%). The solution was stirred at r.t. for 5 min. Then, a solution of allyl sulfone (0.30 mmol in 1.0 mL of toluene,
1 equiv), a solution of aryl halide (0.36 mmol in 500 L of toluene, 1.2 equiv.), TBAB (0.60 mmol, 2 equiv), and KOt-Bu (0.60 mmol, 2 equiv) were successively added. The resulting system was stirred at reflux for 16 h. Then, after cooling to r.t., a sat. aq NH₄Cl solution (3 mL) were added, and the aqueous phase was extracted three times with CH₂Cl₂.
The collected organic layers were dried over anhyd MgSO₄, and the solvent was removed under reduced pressure. The crude product was purified by flash chromatography.