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

Gaëtan Le Duc; Elise Bernoud; Guillaume Prestat; Sandro Cacchi; Giancarlo Fabrizi; Antonia Iazzetti; David Madec; Giovanni Poli

doi:10.1055/s-0031-1289880

LETTER

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

Gaëtan Le Duc^a, Elise Bernoud^a, Guillaume Prestat^a, Sandro Cacchi^b, Giancarlo Fabrizi^b, Antonia Iazzetti^b, 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;

Abstract

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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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References

References and Notes

<A NAME="RB17111ST-1">1</A> Grossert JS. In The chemistry of Sulfones and Sulfoxides Patai S. Rapoport Z. Stirling CJM. John Wiley and Sons; Chichester: 1988.

<A NAME="RB17111ST-2">2</A> For a review, see: Alba A.-R. Companyó X. Rios R. Chem. Soc. Rev. 2010, 39: 2018

<A NAME="RB17111ST-3A">3a</A> Otzen T. Wempe EG. Kunz B. Bartels R. Lehwark-Yvetot G. Hänsel W. Schaper K.-J. Seydel JK. J. Med. Chem. 2004, 47: 240

<A NAME="RB17111ST-3B">3b</A> 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

<A NAME="RB17111ST-4">4</A> Simpkins NS. Sulfones in Organic Synthesis Pergamon Press; Oxford: 1993.

<A NAME="RB17111ST-5A">5a</A> Gais H.-J. Jagusch T. Spalthoff N. Gerhards F. Frank M. Raabe G. Chemistry 2003, 9: 4202

<A NAME="RB17111ST-5B">5b</A> Jagusch T. Gais H.-J. Bondarev O. J. Org. Chem. 2004, 69: 2731

For examples of Pd-catalyzed aromatic sulfonylation, see:

<A NAME="RB17111ST-6A">6a</A> Cacchi S. Fabrizi G. Goggiamani A. Parisi LM. Org. Lett. 2002, 4: 4719

<A NAME="RB17111ST-6B">6b</A> Cacchi S. Fabrizi G. Goggiamani A. Parisi LM. Bernini R. J. Org. Chem. 2004, 69: 5608

<A NAME="RB17111ST-6C">6c</A> Reeves DC. Rodriguez S. Lee H. Haddad N. Krishnamurthy D. Senanayake CH. Tetrahedron Lett. 2009, 50: 2870

For examples of Cu-catalyzed sulfonylations, see:

<A NAME="RB17111ST-6D">6d</A> Baskin JM. Wang Z. Org. Lett. 2002, 4: 4423

<A NAME="RB17111ST-6E">6e</A> Beaulieu C. Guay D. Wang Z. Evans DA. Tetrahedron Lett. 2004, 45: 3233

<A NAME="RB17111ST-6F">6f</A> Bandgar BP. Bettigeri SV. Phopase J. Org. Lett. 2004, 2105

<A NAME="RB17111ST-6G">6g</A> Zhu W. Ma D. J. Org. Chem. 2005, 70: 2696

<A NAME="RB17111ST-6H">6h</A> Huang F. Batey RA. Tetrahedron 2007, 63: 7667

<A NAME="RB17111ST-6I">6i</A> Kir A. Sayyed IA. Lo WF. Kaiser HM. Beller M. Tse MK. Org. Lett. 2007, 9: 3405

<A NAME="RB17111ST-6J">6j</A> Kantam ML. Neelima B. Sreedhar B. Chakravarti R. Synlett 2008, 1455

<A NAME="RB17111ST-7A">7a</A> Bernoud E. Le Duc G. Bantreil X. Prestat G. Madec D. Poli G. Org. Lett. 2010, 12: 320

<A NAME="RB17111ST-7B">7b</A> Maitro G. Prestat G. Madec D. Poli G. Tetrahedron: Asymmetry 2010, 21: 1075

For other uses of in situ generated sulfenate anions in Pd catalysis, see:

<A NAME="RB17111ST-8A">8a</A> Maitro G. Vogel S. Sadaoui M. Prestat G. Madec D. Poli G. Org. Lett. 2007, 9: 5493

<A NAME="RB17111ST-8B">8b</A> Maitro G. Vogel S. Prestat G. Madec D. Poli G. Org. Lett. 2006, 8: 5951

<A NAME="RB17111ST-8C">8c</A> Maitro G. Prestat G. Madec D. Poli G. J. Org. Chem. 2006, 71: 7449

For some examples concerning the use of allylic sulfones in palladium-catalyzed allylic alkylation, see:

<A NAME="RB17111ST-9A">9a</A> Trost BM. Schmuff NR. Miller JM. J. Am. Chem. Soc. 1980, 102: 5979

<A NAME="RB17111ST-9B">9b</A> Clayden J. Julia M. J. Chem. Soc., Chem. Commun. 1994, 1905

<A NAME="RB17111ST-9C">9c</A> Orita A. Watanabe A. Tsuchiya H. Otera J. Tetrahedron 1999, 55: 2889

<A NAME="RB17111ST-9D">9d</A> Cheng W.-C. Halm C. Evarts JB. Olmstead MM. Kurth MJ. J. Org. Chem. 1999, 64: 8557

<A NAME="RB17111ST-9E">9e</A> Deng K. Chalker J. Yang A. Cohen T. Org. Lett. 2005, 7: 3637

<A NAME="RB17111ST-9F">9f</A> The Tuong MB. Sottocornola S. Prestat G. Broggini G. Madec D. Poli G. Synlett 2007, 1521

<A NAME="RB17111ST-10A">10a</A> Itoh T. Mase T. Org. Lett. 2004, 6: 4587

<A NAME="RB17111ST-10B">10b</A> Perrio S. Mispelaere-Canivet C. Spindler J.-F. Beslin P. Tetrahedron 2005, 61: 5253

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

<A NAME="RB17111ST-12">12</A> Poli G. Giambastiani G. J. Org. Chem. 2002, 67: 9456

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.

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