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Synlett 2011(20): 2943-2946  
DOI: 10.1055/s-0031-1289880
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Gaëtan Le Duca, Elise Bernouda, Guillaume Prestata, Sandro Cacchib, Giancarlo Fabrizib, Antonia Iazzettib, David Madec*c, Giovanni Poli*a
a UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire (UMR CNRS 7201), FR 2769, case 183, 4 Place Jussieu, 75005 Paris, France
Fax: +33(01)44277360; e-Mail: giovanni.poli@upmc.fr;
b Dipartimento di Chimica e Tecnologie del Farmaco, La Sapienza, Universita di Roma, P.le A. Moro 5, 00185 Rome, Italy
Fax: +39(06)49912780; e-Mail: sandro.cacchi@uniroma1.it;
c Université de Toulouse, UPS, CNRS, LHFA UMR 5069, bât. 2R1, 118 route de Narbonne, 31062 Toulouse, France
Fax: +33(0)561558204; e-Mail: madec@chimie.ups-tlse.fr;
Further Information

Publication History

Received 3 September 2011
Publication Date:
11 November 2011 (online)

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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.

Key words

sulfones - sulfinate anions - catalysis - palladium - domino reaction

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11

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

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.