Efficient Solvent-Free Synthesis of Homoallylic Alcohols Mediated by Zinc-Copper Couple

Wenjun Zhou; Wenjun Yan; Jin-Xian Wang; Kehu Wang

doi:10.1055/s-2007-1000840

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Synlett 2008(1): 137-141
DOI: 10.1055/s-2007-1000840

LETTER

Efficient Solvent-Free Synthesis of Homoallylic Alcohols Mediated by Zinc-Copper Couple

Wenjun Zhou^a, Wenjun Yan^a, Jin-Xian Wang*^a,b, Kehu Wang^a
^a Institute of Chemistry, Department of Chemistry, Northwest Normal University, 967 An Ning Road (E.), Lanzhou 730070, P. R. of China
Fax: +86(931)7768159; e-Mail: Wangjx@nwnu.edu.cn;
^b State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China

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Publication History

Received 17 September 2007
Publication Date:
11 December 2007 (online)

Abstract
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Abstract

Under solvent-free conditions, it was found that zinc-copper couple could efficiently mediate the Barbier-type reaction of ketones and allyl bromide to give the corresponding homoallylic alcohols in high to excellent yields at room temperature.

Key words

solvent-free - zinc-copper couple - ketones - allylation - homoallylic alcohols

References and Notes

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20

Preparation of the Zinc-Copper Couple: Zinc powder (11.6 g) and distilled H₂O (80 mL) were placed into a 100-mL round-bottom flask equipped with a stir bar. With stirring, HCl acid (37%, 2 × 1 mL) was added over 10 min. Then the CuSO₄ solution (20%, 20 mL) was added dropwise with stirring and the stirring was continued for about 15 min. Finally, the mixture was filtered and the solid was washed with H₂O (3 × 30 mL), acetone (3 × 10 mL), and Et₂O (2 × 10 mL). Then the solid was transferred into a flask equipped with vacuum take-off and dried under vacuum for 3 h at 100 °C. Other M-Cu couples were also prepared in this way.Preparation of the Homoallylic Alcohols: Zinc-copper couple (0.24 g), allyl bromide (2.5 mmol) and ketones (2 mmol) were placed in a dried round-bottom flask, and the mixture was stirred at r.t. and the reaction was monitored by TLC. After reaction completed, sat. brine (10 mL) was poured into the mixture, the mixture was extracted with Et₂O (3 × 10 mL) and the organic layer was separated, dried over anhyd MgSO₄, filtered, and evaporated. The pure products were obtained by flash chromatography over silica gel, and characterized by IR, ¹H NMR, ¹³C NMR and MS.

21

Representative Spectroscopic Data for Compounds 3. Compound 3i: IR: 3475, 2976, 1670, 1456, 1269, 1101, 920, 771, 738 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.24-7.84 (m, 7 H), 5.60-5.70 (m, 1 H), 5.09-5.19 (m, 2 H), 3.88 (q, J = 6.4 Hz, 2 H), 2.65-2.76 (m, 1 H), 2.52-2.63 (m, 1 H), 2.14 (s, 1 H), 1.61 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 146.4, 143.3, 143.3, 141.4, 140.2, 133.7, 126.7, 126.5, 125.0, 123.4, 121.5, 119.8, 119.4, 73.8, 48.6, 37.0, 30.1, 26.8. EI-MS: m/z (%) = 250 (2.4) [M⁺], 209 (64.9), 193 (16.8), 165 (37.7), 43 (100), 39 (17.2). Anal. Calcd for C₁₈H₁₈O: C, 86.36; H, 7.25. Found: C, 86.36; H, 7.36. Compound 3p: IR: 3406, 3077, 2977, 1644, 1439, 1372, 1114, 923, 796 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.88 (d, J = 3.6 Hz, 1 H), 6.63 (d, J = 3.6 Hz, 1 H), 5.67-5.78 (m, 1 H), 5.12-5.19 (m, 2 H), 2.57-2.67 (m, 1 H), 2.48-2.54 (m, 1 H), 2.34 (s, 1 H), 1.57 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 154.6, 132.8, 129.5, 122.5, 120.2, 110.5, 73.0, 48.7, 30.1. EI-MS: m/z (%) = 248 (0.3) [M⁺ + 2], 246 (0.2) [M⁺], 231 (0.3) [M⁺ - Me], 229 (0.3) [M⁺ - OH], 207 (33.7), 43 (100), 39 (21.7). Anal. Calcd for C₉H₁₁BrOS: C, 43.74; H, 4.49. Found: C, 43.29; H, 3.93. Compound 3q: IR: 3439, 3072, 2922, 1662, 1445, 1369, 1142, 917, 829 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.54 (s, 1 H), 5.67-5.78 (m, 1 H), 5.12-5.17 (m, 2 H), 2.15-2.50 (m, 8 H), 2.04 (s, 1 H), 1.51 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 142.1, 134.2, 133.9, 131.3, 125.3, 119.2, 73.6, 47.7, 30.9, 29.3, 15.0. EI-MS: m/z (%) = 196 (2.37) [M⁺], 181 (0.04) [M⁺ - OH], 155 (24.9), 139 (10.5), 113 (5.7), 59 (9.3), 43 (100), 41 (16.2), 39 (16.9). Anal. Calcd for C₁₁H₁₆OS: C, 67.30; H, 8.22. Found: C, 66.92; H, 8.07. Compound 3r: IR: 3411, 3077, 2981, 1684, 1373, 1097, 921, 786 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.05 (s, 1 H), 5.87 (s, 1 H), 5.68-5.72 (m, 1 H), 5.11-5.15 (m, 2 H), 2.64-2.69 (m, 1 H), 2.51-2.56 (m, 1 H), 2.28 (s, 3 H), 2.14 (s, 1 H), 1.51 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 157.3, 151.2, 133.5, 119.0, 105.8, 105.3, 70.5, 46.0, 26.3, 13.5. EI-MS: m/z (%) = 166 (0.7) [M⁺], 149 (1.7) [M⁺ - OH], 135 (0.7), 125 (91.5), 109 (10.3), 95 (2.1), 43 (100), 39 (20.6). Anal. Calcd for C₁₀H₁₄O₂: C, 72.26; H, 8.49. Found: C, 72.28; H, 8.64.