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Synlett 2010(7): 1110-1114  
DOI: 10.1055/s-0029-1219587
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Immobilization of TEMPO Derivatives in Saponite and Use of These Novel Hybrid Materials as Reusable Catalysts

Caren Röbena, Armido Studer*a, Wilhelm L. Hemmeb, Hellmut Eckert*b
a Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstr. 40, 48149 Münster, Germany
Fax: +49(251)8336523; e-Mail: studer@uni-muenster.de;
b Institut für Physikalische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstr. 30, 48149 Münster, Germany
e-Mail: eckerth@uni-muenster.de;
Further Information

Publication History

Received 19 January 2010
Publication Date:
16 March 2010 (online)

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Abstract

The letter describes a novel approach for immobilization of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) derivatives by cation-exchange reaction of TEMPO ammonium salts in a commercially available saponite. The organic-inorganic hybrid material is readily prepared and characterized by solid-state ¹H NMR spectroscopy. The hybrid material can be used as recyclable catalyst for oxidation of various alcohols. High catalytic activity for up to 10 runs is obtained. Leaching of the nitroxide salt out of the saponite occurs to a small extent. However, original high activity of the hybrid material can be restored by simply reloading the hybrid material with nitroxide salt by cation exchange.

Key words

alcohol oxidation - 2,2,6,6-tetramethylpiperidine-1-oxyl - TEMPO - catalyst immobilization - catalysis - solid-state NMR spectroscopy

    References

  • Immobilization of catalysts:
  • 1a Fraile JM. García JI. Mayoral JA. Chem. Rev.  2009,  109:  360 
    Google Scholar
  • 1b Trindade AF. Gois PMP. Afonso CAM. Chem. Rev.  2009,  109:  418 
    Google Scholar
  • 1c Akiyama R. Kobayashi S. Chem. Rev.  2009,  109:  594 
    Google Scholar
  • Immobilization of organocatalysts:
  • 2a Benaglia M. Puglisi A. Cozzi F. Chem. Rev.  2003,  103:  3401 
    Google Scholar
  • 2b Benaglia M. New J. Chem.  2006,  30:  1525 
    Google Scholar
  • 2c Cozzi F. Adv. Synth. Catal.  2006,  348:  1367 
    Google Scholar
  • 2d Gruttadauria M. Giacalone F. Noto R. Chem. Soc. Rev.  2008,  37:  1666 
    Google Scholar
  • Review on the use of TEMPO in synthesis:
  • 3a Vogler T. Studer A. Synthesis  2008,  1979 
    Google Scholar
  • Reviews on immobilization of catalyst into nanostructured supports, see:
  • 3b Fraile JM. García JI. Herrerías CI. Mayoral JA. Pires E. Chem. Soc. Rev.  2009,  38:  695 
    Google Scholar
  • 3c Fraile JM. García JI. Mayoral JA. Chem. Rev.  2009,  109:  360 
    Google Scholar
  • Immobilization of TEMPO:
  • 4a Bolm C. Fey T. Chem. Commun.  1999,  1795 
    Google Scholar
  • 4b Dijksman A. Arends IWCE. Sheldon RA. Chem. Commun.  2000,  271 
    Google Scholar
  • 4c Fey T. Fischer H. Bachmann S. Albert K. Bolm C. J. Org. Chem.  2001,  66:  8154 
    Google Scholar
  • 4d Dijksman A. Arends IWCE. Sheldon RA. Synlett  2001,  102 
    Google Scholar
  • 4e Weik S. Nicholson G. Jung G. Rademann J. Angew. Chem. Int. Ed.  2001,  40:  1436 
    Google Scholar
  • 4f Ciriminna R. Bolm C. Fey T. Pagliaro M. Adv. Synth. Catal.  2002,  344:  159 
    Google Scholar
  • 4g Ansari IA. Gree R. Org. Lett.  2002,  4:  1507 
    Google Scholar
  • 4h Testa ML. Ciriminna R. Hajji C. Garcia EZ. Ciclosi M. Arques JS. Pagliaro M. Adv. Synth. Catal.  2004,  346:  655 
    Google Scholar
  • 4i Ferreira P. Phillips E. Rippon D. Tsang SC. Hayes W. J. Org. Chem.  2004,  69:  6851 
    Google Scholar
  • 4j Pozzi G. Cavazzini M. Quici S. Benaglia M. Dell’Anna G. Org. Lett.  2004,  6:  441 
    Google Scholar
  • 4k Ferreira P. Hayes W. Phillips E. Rippon D. Tsang SC. Green Chem.  2004,  6:  310 
    Google Scholar
  • 4l Gilhespy M. Lok M. Baucherel X. Chem. Commun.  2005,  1085 
    Google Scholar
  • 4m Jiang N. Ragauskas A. Tetrahedron Lett.  2005,  46:  3323 
    Google Scholar
  • 4n Holczknecht O. Cavazzini M. Quici S. Shepperson I. Pozzi G. Adv. Synth. Catal.  2005,  347:  677 
    Google Scholar
  • 4o Benaglia M. Puglisis A. Holczknecht O. Quici S. Pozzi G. Tetrahedron  2005,  61:  12058 
    Google Scholar
  • 4p Geneste F. Moinet C. Ababou-Girard S. Solal F. New J. Chem.  2005,  29:  1520 
    Google Scholar
  • 4q Kubota J. Ido T. Kuroboshi M. Tanaka H. Uchida T. Shimamura K. Tetrahedron  2006,  62:  4769 
    Google Scholar
  • 4r Vugts DJ. Veum L. al-Mafraji K. Lemmens R. Schmitz RF. de Kanter FJJ. Groen MB. Hanefeld U. Orru RVA. Eur. J. Org. Chem.  2006,  1672 
    Google Scholar
  • 4s Gheorghe A. Cuevas-Yañez E. Horn J. Bannwarth W. Narsaiah B. Reiser O. Synlett  2006,  2767 
    Google Scholar
  • 4t Gheorghe A. Matsuno A. Reiser O. Adv. Synth. Catal.  2006,  348:  1016 
    Google Scholar
  • 4u Luo J. Pardin C. Lubell WD. Zhu XX. Chem. Commun.  2007,  2136 
    Google Scholar
  • 4v Mason BP. Bogdan AR. Goswami A. McQuade DT. Org. Lett.  2007,  9:  3449 
    Google Scholar
  • 4w Karimi B. Biglari A. Clark JH. Budarin V. Angew. Chem. Int. Ed.  2007,  46:  7210 
    Google Scholar
  • 4x Gheorghe A. Chinnusamy T. Cuevas-Yañez E. Hilgers P. Reiser O. Org. Lett.  2008,  10:  4171 
    Google Scholar
  • 4y Dobbs AP. Penny MJ. Jones P. Tetrahedron Lett.  2008,  49:  6955 
    Google Scholar
  • 4z Subhani MA. Beigi M. Eilbracht P. Adv. Synth. Catal.  2008,  350:  2903 
    Google Scholar
  • 5a Schätz A. Grass RN. Stark WJ. Reiser O. Chem. Eur. J.  2008,  14:  8262 
    Google Scholar
  • 5b Kuroboshi M. Goto K. Tanaka H. Synthesis  2009,  903 
    Google Scholar
  • 5c Lindner J.-PB. Röben C. Studer A. Stasiak M. Ronge R. Greiner A. Wendorff H.-J. Angew. Chem. Int. Ed.  2009,  48:  8874 
    Google Scholar
  • Intercalation of cationic nitroxides in clays:
  • 6a Grauer Z. Waterman KC. Turro NJ. Langmuir  1987,  3:  59 
    Google Scholar
  • 6b Fujita W. Awaga K. J. Chem. Soc., Chem. Commun.  1995,  739 
    Google Scholar
  • 6c Caneschi A. Gatteschi D. Sangregorio C. Vaz MGF. Costantino U. Nocchetti M. Vivani R. Inorg. Chim. Acta  2002,  338:  127 
    Google Scholar
  • 6d Miwa Y. Drews AR. Schlick S. Macromolecules  2006,  39:  3304 
    Google Scholar
  • 7 Rey P. Rassat A. Nouv. J. Chim.  1983,  7:  531 
    Google Scholar
  • 8 Hemme WL. Fujita W. Awaga K. Eckert H. Dalton Trans.  2009,  7995 
    CrossrefGoogle Scholar
  • 9 Grim RE. Applied Clay Mineralogy   McGraw-Hill; New York: 1962. 
    Google Scholar
  • 10 Anelli PL. Biffi C. Montanari F. Quici S. J. Org. Chem.  1987,  52:  2559 
    CrossrefGoogle Scholar