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DOI: 10.1055/s-2003-39292
A General, Polymer-Supported Acid Catalyzed Hetero-Michael Addition
Publication History
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®
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Kobayashi S.Kakumoto K.Sugiura M. Org. Lett. 2002, 4: 1319 - 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
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Ishihara K.Hasegawa A.Yamamoto H. Angew. Chem. Int. Ed. 2001, 40: 4077
References
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.
12The ion exchange capacity of Nafion® SAC-13 is 0.12 mmolg-1 according to ref. [9b]
14Only 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] ).
15Catalyst 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.