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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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Publication History

Received 7 April 2003
Publication Date:
20 May 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

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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.