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Synlett 2009(1): 89-91  
DOI: 10.1055/s-0028-1087489
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Mild Stereoselective Hydrohalogenation Leading to (Z)-Halopropenamides at Room Temperature

Laurence Feray*, Patricia Perfetti, Michèle P. Bertrand*
Laboratoire de Chimie Moléculaire Organique, UMR 6264 LCP, boite 562, Universités Aix-Marseille 1,2,3, Faculté des Sciences et Techniques de Saint Jérôme, Av. Escadrille Normandie Niemen, 13397 Marseille Cedex 20, France
e-Mail: laurence.feray@univ-cezanne.fr; e-Mail: michele.bertrand@univ-cezanne.fr.;
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Publication History

Received 10 July 2009
Publication Date:
12 December 2008 (online)

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Abstract

Hydroiodination of 2-propynamides leading stereoselectively to (Z)-iodopropenamides was achieved under mild conditions at room temperature by the combined use of zinc iodide and tert­butyl iodide. Similarly, the use of zinc bromide in the presence of tert-butyl bromide enabled the synthesis of (Z)-bromopropen­amides. (Z)-Halopropenoic esters were also prepared in high yields.

Key words

hydrohalogenation - (Z)-halopropenamides - (Z)-halopropenoic esters - tert-butyl halide - zinc halide

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9

The reactions were generally performed at 90 ˚C over 22-48 h. At 70 ˚C lower yields were obtained (see ref. 8b).

11

Using only 2 equivalents of tert-butyl iodide led to lower yields.

13

This might be correlated to the relative basicity of amides and sulfoxides.

14

( Z )- N , N -Diallyl-3-iodoacrylamide(2d); Typical Procedure To a solution of N,N-diallyl-3-propynamide (50 mg, 0.335 mmol) in CH2Cl2 (1.7 mL) were added t-BuI (200 µL, 1.67 mmol, 3 equiv) and ZnI2 (214 mg, 0.67 mmol, 2 equiv) at r.t. After 18 h, H2O (5 mL) was added, and the reaction mixture was extracted twice with CH2Cl2. The organic layers were dried over MgSO4, filtered, and concentrated under reduce pressure. Flash chromatography on SiO2 (100% pentane then 100% Et2O) afforded 2d (81 mg, 0.293 mmol, 87%). ¹H NMR (300 MHz): δ = 3.85 (br d, J = 5.1 Hz, 2 H), 4.05 (br d, J = 5.9 Hz, 2 H), 5.11-5.28 (m, 4 H), 5.68-5.89 (m, 2 H), 6.85 (d, J = 8.8 Hz, 1 H), 7.10 (d, J = 8.8 Hz, 1 H). ¹³C NMR (75 MHz): δ = 47.4 (CH2), 49.9 (CH2), 87.6 (=CHI), 117.9 (=CH2), 118.4 (=CH2), 132.9 (=CH), 133.1 (=CH), 134.5 (=CH), 167.1 (C=O). HRMS: m/z calcd for C9H12NOI [MH]+: 278.0036; found: 278.0035.

16

Owing to complexation of the product to zinc salts, the olefinic protons are more deshielded in the crude reaction mixture - before aqueous treatment - than in the pure isolated product 2d (δ = 7.0 ppm and 7.4 ppm with a coupling constant equal to 9.1 Hz: 6.85 ppm and 7.10 ppm with a coupling constant equal to 8.8 Hz, respectively).

17

Using zinc bromide led to degradation of benzylic and propargylic esters.