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Synlett 2003(7): 1070-1072
DOI: 10.1055/s-2003-39292
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A General, Polymer-Supported Acid Catalyzed Hetero-Michael Addition

Tobias C. Wabnitz, Jin-Quan Yu, Jonathan B. Spencer*
Cambridge University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW, UK
Fax: +44(1223)336362; e-Mail: jbs20@cam.ac.uk;
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Publikationsverlauf

Received 7 April 2003
Publikationsdatum:
20. Mai 2003 (online)

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Abstract

Hetero-Michael additions of nitrogen, oxygen and sulfur nucleophiles to α,β-unsaturated ketones were efficiently catalyzed by Nafion® SAC-13 perfluorinated resinsulfonic acid.

Key words

hetero-Michael additions - heterogeneous catalysis - enones - polymer-support - Nafion®

    References

  • 1 Ley SV. Baxendale IR. Bream RN. Jackson PS. Leach AG. Longbottom DA. Nesi M. Scott JS. Storer RI. Taylor SJ. J. Chem. Soc., Perkin Trans. 1  2000,  3815 
    Crossref
  • Recent examples:
  • 2a Nagayama S. Kobayashi S. Angew. Chem. Int. Ed.  2000,  39:  567 
    CrossrefSuche in Google Scholar
  • 2b Kobayashi S. Nagayama S. Synlett  1997,  653 
    Crossref
  • 2c Kobayashi S. Nagayama S. J. Am. Chem. Soc.  1998,  120:  2985 
    CrossrefSuche in Google Scholar
  • 3 Villemin D. Martin B. J. Chem. Res.  1994,  146 
  • 4 Sercheli R., Ferreira A. L. B., Guerreiro M. C., Vargas R. M., Sheldon R. A., Schuchardt U.; Tetrahedron Lett.; 1997, 38: 1325
  • Recent developments:
  • 5a Choudary BM. Kantam ML. Reddy CRV. Rao KK. Figueras F. J. Mol. Cat. A  1999,  146:  279 
    CrossrefSuche in Google Scholar
  • 5b Zahouily M. Abrouki Y. Rayadh A. Sebti S. Dhimane H. David M. Tetrahedron Lett.  2003,  44:  2463 
    CrossrefSuche in Google Scholar
  • 6a Pelletier SW. Venkov AP. Finer-Moore J. Mody N. Tetrahedron Lett.  1980,  21:  809 
    Suche in Google Scholar
  • 6b Cornelis A. Laszlo P. Synlett  1994,  155 
  • 6c Shaikh NS. Deshpande VH. Bedekar AV. Tetrahedron  2001,  57:  9045 
    Suche in Google Scholar
  • 6d Sundararajan G. Prabagaran N. Org. Lett.  2001,  3:  389 
    Suche in Google Scholar
  • 6e Bartoli G. Bosco M. Marcantoni E. Petrini M. Sambri L. Torregiani E. J. Org. Chem.  2001,  66:  9052 
    Suche in Google Scholar
  • 6f Lorette NB. J. Org. Chem.  1958,  23:  937 
    Suche in Google Scholar
  • 6g Kabashima H. Katou T. Hattori H. Appl. Cat. A  2001,  214:  121 
    Suche in Google Scholar
  • 7 Wabnitz TC. Spencer JB. Org. Lett.  2003,  5:  in press 
    Suche in Google Scholar
  • 8a Olah GA. Iyer PS. Prakash GKS. Synthesis  1986,  513 
  • 8b Harmer MA. Sun Q. Appl. Cat. A  2001,  221:  45 
    Suche in Google Scholar
  • 9a Török B. Kiricsi I. Molnar A. Olah GA. J. Cat.  2000,  193:  132 
    Suche in Google Scholar
  • 9b Heidekum A. Harmer MA. Hoelderich WF. J. Cat.  1999,  181:  217 
    Suche in Google Scholar
  • 11 Hayashi Y. Nishimura K. Chem. Lett.  2002,  296 
    Crossref
  • 13a Gaunt MJ. Spencer JB. Org. Lett.  2001,  3:  25 
    CrossrefPubMedSuche in Google Scholar
  • 13b Wabnitz TC. Spencer JB. Tetrahedron Lett.  2002,  43:  3891 
    CrossrefPubMedSuche in Google Scholar
  • 13c Kobayashi S. Kakumoto K. Sugiura M. Org. Lett.  2002,  4:  1319 
    CrossrefPubMedSuche in Google Scholar
  • 16 Analytical data for 5-(benzyloxycarbonylamino)hexan-3-one: 1H NMR (400 MHz, CDCl3): δ = 1.00 (t, J = 7.3 Hz, 3 H), 1.19 (d, J = 6.7 Hz, 3 H), 2.38 (q, J = 7.3 Hz, 2 H), 2.53 (dd, J = 5.9 Hz, 15.7 Hz, 1 H), 1.65 (dd, J = 4.8 Hz, 15.7 Hz, 1 H), 4.00-4.10 (m, 1 H), 5.05 (s, 2 H), 5.33 (br, 1 H), 7.22-7.38 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ = 7.9, 20.9 (CH3), 36.9 (CH2), 44.3 (CH), 48.2, 66.9 (CH2), 128.4, 128.7, 129.9 (Ar-C), 137.0 (ipso-Ar-C), 156.0, 210.5 (C=O). IR (neat, film): cm-1 3323, 3061, 2975, 1706, 1680, 1534, 1254. HRMS [+ESI]: calc. 272.1263, found: 272.1250 ([C14H19NO3Na]+). Mp: 55-57 °C
  • 17 Ishihara K. Hasegawa A. Yamamoto H. Angew. Chem. Int. Ed.  2001,  40:  4077 
    CrossrefSuche in Google Scholar
10

Experimental procedure: Enone (0.25 mmol) and nucleophile (0.375 mmol, 1.5 equiv.) were dissolved in CH3CN (0.5 mL) and stirred over Nafion® SAC-13 (15 mg, 60 g˙mol-1) at room temperature. The reaction was monitored by TLC and the product was isolated by preparative TLC after filtering off the catalyst.

12

The ion exchange capacity of Nafion® SAC-13 is 0.12 mmolg-1 according to ref. [9b]

14

Only sluggish conversion was observed with acetacrylimide and benzyl carbamate: 34% yield (48 h) with Pd(CH3CN)4(BF4)2; 84% yield (72 h) with Tf2NH (see ref. [7] ).

15

Catalyst regeneration: Spent Nafion® SAC-13 was stirred over 6 N HCl (0.5 mL) overnight. After filtration, the catalyst was dried in vacuo for 20 h and reused.