Iron-Catalyzed Coupling Reaction between 1,1-Dichloro-1-alkenes and Grignard Reagents

Mickaël Dos Santos; Xavier Franck; Reynald Hocquemiller; Bruno Figadère; Jean-François Peyrat; Olivier Provot; Jean-Daniel Brion; Mouâd Alami

doi:10.1055/s-2004-835626

LETTER

Iron-Catalyzed Coupling Reaction between 1,1-Dichloro-1-alkenes and Grignard Reagents

Mickaël Dos Santos^a, Xavier Franck^a, Reynald Hocquemiller^a, Bruno Figadère*^a, Jean-François Peyrat^b, Olivier Provot^b, Jean-Daniel Brion^b, Mouâd Alami*^b
^a Laboratoire de Pharmacognosie, BioCIS - CNRS (UMR 8076), Université Paris-Sud, Faculté de Pharmacie, rue Jean-Baptiste Clément, 92296 Châtenay-Malabry, France
Fax: +33(1)46835399; e-Mail: bruno.figadere@cep.u-psud.fr;
^b Laboratoire de Chimie Thérapeutique, BioCIS - CNRS (UMR 8076), Université Paris-Sud, Faculté de Pharmacie, rue Jean-Baptiste Clément, 92296 Châtenay-Malabry, France
e-Mail: mouad.alami@cep.u-psud.fr;

Abstract

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Abstract

This letter reports the coupling reaction of Grignard reagents with 1,1-dichloro-1-alkenes in the presence of the environmentally friendly iron(III) catalyst. This non-toxic procedure is general and provides the di-coupled products as the major compounds. The scope and limitations of this new reaction are described.

Key words

Grignard reagents - iron - 1,1-dichloro-1-alkenes - tri-substituted alkenes

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Referenzen

References

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13

Typical Procedure and Selected Spectroscopic Data: In a round-bottomed flask, under a nitrogen atmosphere, containing the 1,1-dichloro-1-alkene (1.00 mmol) and Fe(acac)₃ (35.3 mg, 0.10 mmol) was added THF (1.2 mL). The reaction mixture was cooled to -30 °C and the desired Grignard reagent (3.00 mmol of typically 1 M solution in THF) was added dropwise. The red colored solution turned dark brown to black (depending on the Grignard reagent). The reaction mixture was stirred for 1.5 h to 18 h, until the disappearance of starting material as judged by TLC. A 1 M aq HCl solution (5.0 mL) was then added, and the two layers were separated. After extraction of the organic layer by EtOAc (2 × 20 mL), the combined organic layers were washed three times with H₂O, then dried over MgSO₄, filtered, and concentrated under vacuum. The crude residue was then purified by silica gel column chromatography to yield the expected adducts (see in the text for yields).
1,1-Dibutyl-2-(4-methoxyphenyl)ethylene (2): ¹H NMR (200 MHz): δ = 7.14 (d, J = 8.7 Hz, 2 H), 6.86 (d, J = 8.8 Hz, 2 H), 6.20 (s, 1 H), 3.81 (s, 3 H), 2.16 (m, 4 H), 1.42 (m, 8 H), 0.94 (t, J = 7.1 Hz, 3 H), 0.90 (t, J = 7.1 Hz, 3 H) ppm. ¹³C NMR (50 MHz): δ = 157.7, 142.6, 131.4, 129.7, 124.1, 113.5, 55.2, 37.1, 30.5, 30.4, 22.9, 22.6, 14.0, 13.9 ppm.
1,1-Dibutyl-2-(2-quinolyl)ethylene (5a): ¹H NMR (200 MHz): δ = 8.04 (d, J = 8.4 Hz, 2 H), 7.74 (d, J = 8.1 Hz, 1 H), 7.66 (td, J = 8.2, 1.1 Hz, 1 H), 7.45 (t, J = 7.4 Hz, 1 H), 7.30 (d, J = 8.4 Hz, 1 H), 6.47 (s, 1 H), 2.67 (t, J = 7.3 Hz, 2 H), 2.28 (t, J = 6.9 Hz, 2 H), 1.60 (m, 4 H), 1.37 (m, 4 H), 0.97 (t, J = 7.4 Hz, 3 H), 0.93 (t, J = 7.3 Hz, 3 H) ppm. ¹³C NMR (50 MHz): δ = 157.6, 151.3, 148.0, 135.4, 129.2, 129.1, 127.2, 126.2, 125.6, 124.4, 122.4, 38.1, 31.3, 30.6, 30.3, 23.0, 22.6, 14.0, 13.9 ppm. ESI-MS: m/z (%) = 268 (100) [MH⁺].
1,1-Diethyl-2-(2-quinolyl)ethylene (5b): ¹H NMR (200 MHz): δ = 8.07 (d, J = 6.9 Hz, 1 H), 8.02 (d, J = 6.4 Hz, 1 H), 7.73 (d, J = 8.1 Hz, 1 H), 7.66 (td, J = 7.1, 1.5 Hz, 1 H), 7.45 (t, J = 7.4 Hz, 1 H), 7.31 (d, J = 8.6 Hz, 1 H), 6.47 (br s, 1 H), 2.65 (q, J = 7.6 Hz, 2 H), 2.30 (qd, J = 7.4, 1.1 Hz, 2 H), 1.19 (t, J = 7.2 Hz, 3 H), 1.16 (t, J = 7.3 Hz, 3 H) ppm. ¹³C NMR (50 MHz): δ = 157.5, 153.4, 147.8, 135.6, 129.2, 129.0, 127.2, 126.2, 125.6, 123.1, 122.2, 30.3, 24.6, 12.9, 12.5 ppm. ESI-MS: m/z (%) = 234 (35) {M + Na⁺], 212 (100) [MH⁺].
1,1-Di- p -toluyl-2-(2-quinolyl)ethylene (5c): ¹H NMR (200 MHz): δ = 8.04 (d, J = 8.8 Hz, 1 H), 7.72 (d, J = 8.7 Hz, 1 H), 7.64 (m, 2 H), 7.44 (t, J = 7.3 Hz, 1 H), 7.31 (m, 3 H), 7.15 (m, 6 H), 6.84 (d, J = 8.8 Hz, 1 H), 2.40 (s, 3 H), 2.38 (s, 3 H) ppm. ¹³C NMR (50 MHz): δ = 157.5, 148.1, 147.3, 139.8, 138.1, 137.8, 136.9, 134.7, 130.3, 129.3, 128.9, 128.1, 127.9, 127.3, 126.5, 126.0, 122.0, 21.3, 21.1 ppm. ESI-MS: m/z (%) = 358 (10) [M + Na⁺], 336 (100) [MH⁺].
1,1-Dithienyl-2-yl-2-(2-quinolyl)ethylene (5d): ¹H NMR (200 MHz): δ = 8.03 (d, J = 8.2 Hz, 1 H), 7.80 (d, J = 8.7 Hz, 1 H), 7.69 (d, J = 7.6 Hz, 1 H), 7.65 (dd, J = 7.1, 1.6 Hz, 1 H), 7.45 (m, 3 H), 7.32 (dd, J = 5.0, 1.9 Hz, 1 H), 7.08 (s, 1 H), 7.05 (m, 3 H), 6.91 (d, J = 8.7 Hz, 1 H) ppm. ¹³C NMR (50 MHz): δ = 156.1, 147.9, 146.4, 139.3, 135.0, 133.1, 129.4, 129.1, 129.0, 128.9, 127.5, 127.4, 127.3, 127.1, 126.6, 126.5, 126.4, 121.5 ppm. ESI-MS: m/z (%) = 342 (15) [M + Na], 320 (100) [MH⁺].
1,1-Cyclohexyliden-2-(2-quinolyl)ethylene (5e): ¹H NMR (200 MHz): δ = 8.05 (d, J = 8.5 Hz, 2 H), 7.75 (d, J = 7.9 Hz, 1 H), 7.67 (td, J = 8.3, 1.3 Hz, 1 H), 7.46 (t, J = 7.8 Hz, 1 H), 7.32 (d, J = 8.5 Hz, 1 H), 6.48 (s, 1 H), 2.75 (m, 2 H), 2.36 (t, J = 5.6 Hz, 2 H), 1.66 (m, 6 H) ppm. ¹³C NMR (50 MHz): δ = 157.6, 149.9, 147.9, 135.7, 129.3, 129.1, 127.3, 126.3, 125.8, 122.6, 122.4, 38.1, 29.9, 28.6, 27.8, 26.5 ppm. ESI-MS: m/z (%) = 224 (100) [MH⁺].
4-Benzyloxy-1,1-dibutylbut-1-ene (8a): ¹H NMR (200 MHz): δ = 7.36 (m, 5 H), 5.13 (br t, J = 7.0 Hz, 1 H), 4.53 (s, 2 H), 3.47 (t, J = 7.2 Hz, 2 H), 2.36 (q, J = 7.1 Hz, 2 H), 2.00 (m, 4 H), 1.33 (m, 8 H), 0.91 (t, J = 6.8 Hz, 6 H) ppm. ¹³C NMR (50 MHz): δ = 142.0, 138.7, 128.3, 127.6, 127.4, 119.9, 72.8, 70.5, 36.6, 30.7, 30.4, 30.0, 28.5, 22.9, 22.5, 14.0 ppm. ESI-MS: m/z (%) = 297 (81) [M + Na⁺], 275 (16) [MH⁺].
4-Benzyloxy-1,1-didodecylbut-1-ene (8b): ¹H NMR (200 MHz): δ = 7.34 (m, 5 H), 5.12 (br t, J = 7.0 Hz, 1 H), 4.56 (s, 2 H), 3.46 (t, J = 7.2 Hz, 2 H), 2.35 (q, J = 7.1 Hz, 2 H), 2.00 (m, 4 H), 1.27 (m, 40 H), 0.89 (t, J = 6.4 Hz, 6 H) ppm. ¹³C NMR (50 MHz): δ = 142.1, 138.7, 128.3, 127.6, 127.4, 119.9, 72.8, 70.5, 37.0, 31.9, 29.8, 29.7, 29.5, 29.4, 28.5, 28.2, 22.7, 14.1 ppm. ESI-MS: m/z (%) = 499 (100) [MH⁺].