Palladium-Catalyzed Desulfitative Mizoroki-Heck Coupling Reactions of Sulfonyl Chlorides with Olefins in a Nitrile-Functionalized Ionic Liquid

 

 Buy Article Permissions and Reprints All articles of this category

Abstract

Aryl and alkenyl sulfonyl chlorides can be used in Heck-Mizoroki-type couplings with mono- and disubstituted olefins in a nitrile-functionalized ionic liquid, viz. [C₃CNpy][Tf₂N]. Advan­tages over previously reported methods include: (1) use of a cheap catalyst source, PdCl₂, (2) ability to handle the catalyst in air, (3) ­reduced reaction times, (4) elimination of phase-transfer catalysts due to the high solubility of the inorganic base in the ionic liquid, and (5) facile recycling of the ionic liquid-palladium catalyst. The yields of coupling products remain in the same range as the reactions conducted in organic solvents. Palladium nanoparticles, characterized using transmission electron microscopy, have been identified in the ionic liquid following the Heck-Mizoroki type ­coupling reactions.

References and Notes

• 1a Mizoroki T. Mori K. Ozaki A. Bull. Chem. Soc. Jpn.  1971,  44:  581 
  Google Scholar
• 1b Heck RF. Nolley JP. J. Org. Chem.  1972,  37:  2320 
  Google Scholar
• For reviews of the Heck reaction, see for example:
• 2a Bräse S. de Meijere A. In Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley; New York: 1998.  Chap. 3.
  CrossrefPubMedGoogle Scholar
• 2b Beletskaya IP. Cheprakov AV. Chem. Rev.  2000,  100:  3009 
  CrossrefPubMedGoogle Scholar
• 2c Heck RF. In Comprehensive Organic Synthesis   Vol. 4:  Trost BM. Pergamon Press; New York: 1991.  Chap. 4.3.
  CrossrefPubMedGoogle Scholar
• 2d Heck RF. Org. React.  1982,  27:  345 
  CrossrefPubMedGoogle Scholar
• 2e Crisp GT. Chem. Soc. Rev.  1998,  27:  427 
  CrossrefPubMedGoogle Scholar
• 2f de Meijere A. Meyer FE. Angew. Chem., Int. Ed. Engl.  1994,  33:  2379 
  CrossrefPubMedGoogle Scholar
• 2g Jeffery T. In Advances in Metal-Organic Chemistry   Vol. 5:  Liebeskind LS. JAI; London: 1996.  p.153-260  
  CrossrefPubMedGoogle Scholar
• 2h Cabri W. Candiani I. Acc. Chem. Res.  1995,  28:  2 
  CrossrefPubMedGoogle Scholar
• 2i Littke AF. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  4176 
  CrossrefPubMedGoogle Scholar
• 2j Hassan J. Sévignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 
  CrossrefPubMedGoogle Scholar
• 2k Metal-Catalyzed Cross-Coupling Reactions   2nd ed.:  de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. 
  CrossrefPubMedGoogle Scholar
• 3 Blaser H.-U. Spencer A. J. Organomet. Chem.  1982,  233:  267 
  CrossrefGoogle Scholar
• For 2-methylprop-2-enesulfonyl chloride preparation, see:
• 4a Bouchez LC. Dubbaka SR. Turks M. Vogel P. J. Org. Chem.  2004,  69:  6413 
  CrossrefGoogle Scholar
• 4b Dubbaka SR. Vogel P. Tetrahedron  2005,  61:  1523 ; and references cited therein
  CrossrefGoogle Scholar
• 5a Dubbaka SR. Vogel P. J. Am. Chem. Soc.  2003,  125:  15292 
  Article in Thieme ConnectGoogle Scholar
• 5b Dubbaka SR. Steunenberg P. Vogel P. Synlett  2004,  1235 
  Article in Thieme ConnectGoogle Scholar
• 6 Dubbaka SR. Vogel P. Org. Lett.  2004,  6:  95 
  CrossrefGoogle Scholar
• 7 Dubbaka SR. Vogel P. Adv. Synth. Catal.  2004,  346:  1793 
  CrossrefGoogle Scholar
• 9 Dubbaka SR. Vogel P. Chem. Eur. J.  2005,  11:  2633 
  CrossrefGoogle Scholar
• 10 For a review, see: Dubbaka SR. Vogel P. Angew. Chem. Int. Ed.  2005,  44:  7674 
  CrossrefPubMedGoogle Scholar
• For a recent review, see for example:
• 11a Ionic Liquids as Green Solvents   Rogers RD. Seddon KR. ACS Symposium Series 856, American Chemical Society; Washington DC: 2003. 
  CrossrefPubMedGoogle Scholar
• 11b Ionic Liquids in Synthesis   Wasserscheid P. Welton T. Wiley-VCH; Weinheim: 2003. 
  CrossrefPubMedGoogle Scholar
• 11c Rooney DW. Seddon KR. In Handbook of Solvents   Wypych G. ChemTech Publishing; Toronto: 2001.  p.1459-1484  
  CrossrefPubMedGoogle Scholar
• 11d Seddon KR. Stark A. Torres M.-J. Pure Appl. Chem.  2000,  72:  2275 
  CrossrefPubMedGoogle Scholar
• 11e Wasserscheid P. Keim W. Angew. Chem. Int. Ed.  2000,  39:  3772 
  CrossrefPubMedGoogle Scholar
• 11f Welton T. Smith PJ. Adv. Organomet. Chem.  2004,  51:  251 
  CrossrefPubMedGoogle Scholar
• 11g Dupont J. de Souza RF. Suarez PAZ. Chem. Rev.  2002,  102:  3667 
  CrossrefPubMedGoogle Scholar
• 11h Dyson PJ. Geldbach T. Metal-Catalysed Reactions in Ionic Liquids, In Catalysis by Metal Complexes   Vol. 29:  Springer; Berlin: 2005. 
  CrossrefPubMedGoogle Scholar
• 12a Chiappe C. Imperato G. Napolitano E. Pieraccini D. Green Chem.  2004,  6:  33 
  CrossrefPubMedGoogle Scholar
• 12b Handy ST. Zhang X. Org. Lett.  2001,  3:  233 
  CrossrefPubMedGoogle Scholar
• 13a Mathews CJ. Smith PJ. Welton T. Chem. Commun.  2000,  1249 
  CrossrefGoogle Scholar
• 13b Liu S. Fukuyama T. Sato M. Ryu I. Synlett  2004,  1814 
  CrossrefGoogle Scholar
• 13c Xiao J.-C. Shreeve JM. J. Org. Chem.  2005,  70:  3072 ; and references cited therein
  CrossrefGoogle Scholar
• 14a Fukuyama T. Shinmen M. Nishitani S. Sato M. Ryu I. Org. Lett.  2002,  4:  1691 
  CrossrefGoogle Scholar
• 14b Thathagar MB. Kooyman PJ. Boerleider R. Jansen E. Eleevier CJ. Rothenberg G. Adv. Synth. Catal.  2005,  347:  1965 
  CrossrefGoogle Scholar
• 15a Kaufmann DE. Nouroozian M. Henze H. Synlett  1996,  1091 
  CrossrefGoogle Scholar
• 15b Carmichael AJ. Earle MJ. Holbrey JD. McCormac PB. Seddon KR. Org. Lett.  1999,  1:  997 
  CrossrefGoogle Scholar
• 15c Böhm VPW. Herrmann WA. Chem. Eur. J.  2000,  6:  3209 
  CrossrefGoogle Scholar
• 15d Park SB. Alper H. Org. Lett.  2003,  5:  1691 
  CrossrefGoogle Scholar
• 15e Mo J. Xu L. Xiao J. J. Am. Chem. Soc.  2005,  127:  751 ; and references cited therein
  CrossrefGoogle Scholar
• 16 Zhao D. Fei Z. Geldbach TJ. Scopelliti R. Dyson PJ. J. Am. Chem. Soc.  2004,  126:  15876 
  CrossrefGoogle Scholar
• 17a Herrmann WA. Brossmer C. Öfele K. Reisinger C.-P. Priermeier T. Beller M. Fischer H. Angew. Chem., Int. Ed. Engl.  1995,  34:  1844 
  CrossrefGoogle Scholar
• 17b Herrmann WA. Brossmer C. Öfele K. Beller M. Fischer H. J. Mol. Catal. A: Chem.  1995,  103:  133 
  CrossrefGoogle Scholar
• 19a Deshmukh RR. Rajagopal R. Srinivasan KV. Chem. Commun.  2001,  1544 
  CrossrefGoogle Scholar
• 19b Dupont J. Fonseca GS. Umpierre AP. Fichtner PFP. Teixeira SR. J. Am. Chem. Soc.  2002,  124:  4228 
  CrossrefGoogle Scholar
• 20 Cassol CC. Umpierre AP. Machado G. Wolke SI. Dupont J. J. Am. Chem. Soc.  2005,  127:  3298 
  CrossrefGoogle Scholar

Dubbaka, S. R.; Vogel, P.; submitted.

General Procedure for Desulfitative Palladium-Catalyzed Mizoroki-Heck Reaction of Sulfonyl Chlorides with Monosubstituted Olefins To a Schlenk tube, the sulfonyl chloride (1 equiv, 1.5 mmol), PdCl₂ (1 mol%, 0.015 mmol), K₂CO₃ (1.5 equiv, 2.25 mmol), Me(Oct)₃NCl (15 mol%, 0.23 mmol) and IL 1 (2 mL) were added. After the mixture was flushed with nitrogen, the olefin (2.0 equiv, 3.0 mmol) was added. The reaction mixture was heated at 140 °C for 1-2 h. After cooling to r.t., the product was extracted with Et₂O (3 × 15 mL). The combined extracts were washed with brine and H₂O and then dried with Na₂SO₄. The coupling product was obtained after removal of solvent. An external standard (diphenylmethane, 0.6 mmol) was used for GC analysis. The ionic liquid phase was washed with Et₂O and placed under vacuum for 18 h prior to the next catalytic cycle.