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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;
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Publikationsverlauf

Received 3 September 2011
Publikationsdatum:
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

    References and Notes

  • 1 Grossert JS. In The chemistry of Sulfones and Sulfoxides   Patai S. Rapoport Z. Stirling CJM. John Wiley and Sons; Chichester: 1988. 
    Google Scholar
  • 2 For a review, see: Alba A.-R. Companyó X. Rios R. Chem. Soc. Rev.  2010,  39:  2018 
    Google Scholar
  • 3a Otzen T. Wempe EG. Kunz B. Bartels R. Lehwark-Yvetot G. Hänsel W. Schaper K.-J. Seydel JK. J. Med. Chem.  2004,  47:  240 
    Google Scholar
  • 3b Jones TR. Webber SE. Varney MD. Reddy MR. Lewis KK. Katharddekar V. Mazdiyasni H. Deal J. Nguyen D. Welsh KM. Webber S. Johnson A. Matthews DA. Smith WW. Janson CA. Bacquet RJ. Howland EF. Booth CLJ. Ward RW. Herrmann SM. White J. Bartlett CA. Morse CA. J. Med. Chem.  1997,  40:  677 
    Google Scholar
  • 4 Simpkins NS. Sulfones in Organic Synthesis   Pergamon Press; Oxford: 1993. 
    Google Scholar
  • 5a Gais H.-J. Jagusch T. Spalthoff N. Gerhards F. Frank M. Raabe G. Chemistry  2003,  9:  4202 
    Google Scholar
  • 5b Jagusch T. Gais H.-J. Bondarev O. J. Org. Chem.  2004,  69:  2731 
    Google Scholar
  • For examples of Pd-catalyzed aromatic sulfonylation, see:
  • 6a Cacchi S. Fabrizi G. Goggiamani A. Parisi LM. Org. Lett.  2002,  4:  4719 
    Google Scholar
  • 6b Cacchi S. Fabrizi G. Goggiamani A. Parisi LM. Bernini R. J. Org. Chem.  2004,  69:  5608 
    Google Scholar
  • 6c Reeves DC. Rodriguez S. Lee H. Haddad N. Krishnamurthy D. Senanayake CH. Tetrahedron Lett.  2009,  50:  2870 
    Google Scholar
  • For examples of Cu-catalyzed sulfonylations, see:
  • 6d Baskin JM. Wang Z. Org. Lett.  2002,  4:  4423 
    Google Scholar
  • 6e Beaulieu C. Guay D. Wang Z. Evans DA. Tetrahedron Lett.  2004,  45:  3233 
    Google Scholar
  • 6f Bandgar BP. Bettigeri SV. Phopase J. Org. Lett.  2004,  2105 
    Google Scholar
  • 6g Zhu W. Ma D. J. Org. Chem.  2005,  70:  2696 
    Google Scholar
  • 6h Huang F. Batey RA. Tetrahedron  2007,  63:  7667 
    Google Scholar
  • 6i Kir A. Sayyed IA. Lo WF. Kaiser HM. Beller M. Tse MK. Org. Lett.  2007,  9:  3405 
    Google Scholar
  • 6j Kantam ML. Neelima B. Sreedhar B. Chakravarti R. Synlett  2008,  1455 
    Google Scholar
  • 7a Bernoud E. Le Duc G. Bantreil X. Prestat G. Madec D. Poli G. Org. Lett.  2010,  12:  320 
    Google Scholar
  • 7b Maitro G. Prestat G. Madec D. Poli G. Tetrahedron: Asymmetry  2010,  21:  1075 
    Google Scholar
  • For other uses of in situ generated sulfenate anions in Pd catalysis, see:
  • 8a Maitro G. Vogel S. Sadaoui M. Prestat G. Madec D. Poli G. Org. Lett.  2007,  9:  5493 
    Google Scholar
  • 8b Maitro G. Vogel S. Prestat G. Madec D. Poli G. Org. Lett.  2006,  8:  5951 
    Google Scholar
  • 8c Maitro G. Prestat G. Madec D. Poli G. J. Org. Chem.  2006,  71:  7449 
    Google Scholar
  • For some examples concerning the use of allylic sulfones in palladium-catalyzed allylic alkylation, see:
  • 9a Trost BM. Schmuff NR. Miller JM. J. Am. Chem. Soc.  1980,  102:  5979 
    Google Scholar
  • 9b Clayden J. Julia M. J. Chem. Soc., Chem. Commun.  1994,  1905 
    Google Scholar
  • 9c Orita A. Watanabe A. Tsuchiya H. Otera J. Tetrahedron  1999,  55:  2889 
    Google Scholar
  • 9d Cheng W.-C. Halm C. Evarts JB. Olmstead MM. Kurth MJ. J. Org. Chem.  1999,  64:  8557 
    Google Scholar
  • 9e Deng K. Chalker J. Yang A. Cohen T. Org. Lett.  2005,  7:  3637 
    Google Scholar
  • 9f The Tuong MB. Sottocornola S. Prestat G. Broggini G. Madec D. Poli G. Synlett  2007,  1521 
    Google Scholar
  • 10a Itoh T. Mase T. Org. Lett.  2004,  6:  4587 
    Google Scholar
  • 10b Perrio S. Mispelaere-Canivet C. Spindler J.-F. Beslin P. Tetrahedron  2005,  61:  5253 
    Google Scholar
  • 12 Poli G. Giambastiani G. J. Org. Chem.  2002,  67:  9456 
    Google Scholar
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.