Synlett 2006(11): 1786-1788  
DOI: 10.1055/s-2006-947320
LETTER
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Synthesis of Vinyl Selenides by Coupling of Vinyl Bromides with Diorgano Diselenides Catalyzed by Copper(I) in [Bmim]BF4

Dezhi Chang, Weiliang Bao*
Department of Chemistry, Zhejiang University, Xi Xi Campus, Hangzhou, Zhejiang 310028, P. R. of China
Fax: +86(571)88273814; e-Mail: wlbao@css.zju.edu.cn;
Further Information

Publication History

Received 25 March 2006
Publication Date:
04 July 2006 (online)

Abstract

The CuI/l-proline-catalyzed zinc-promoted coupling ­reaction of vinyl bromides with diaryl diselenides or dialkyl ­diselenides readily occurred at 110 °C in [Bmim]BF4 to give the corresponding vinyl selenides in good to excellent yields. The ­recyclable catalyst system offered a convenient, stereoselective and versatile method for the synthesis of vinyl selenides.

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Representative Procedure for the Synthesis of (E)-β-Phenylselenostyrene.
CuI (0.057 g, 0.3 mmol), l-proline (0.069 g, 0.6 mmol), Zn (0.098 g, 1.5 mmol) and dry [Bmim]BF4 (2.00 mL) were added to a 10-mL flask. The reaction mixture was stirred and dried by vacuum heating in an oil bath at 110 °C for 0.5 h. Diphenyl diselenide (0.234 g, 0.75 mmol) was added to the stirred mixture, and then (E)-(2-bromovinyl) benzene (0.035 g, 1.65 mmol, 1.1 equiv) was injected into the sealed flask. The reaction was carried out under a nitrogen atmosphere and monitored by TLC. After the reaction, the resulting mixture was cooled to r.t. and extracted with Et2O (3 × 5 mL). The extracts were combined and washed with H2O (2 × 10 mL), and dried over MgSO4. Evaporation of the solvent under reduced pressure gave a dark brown oil, which was further purified by column chromatography (PE), which gave a viscous oil (0.316 g, 83%).This procedure was followed for the synthesis of all products listed in Table [2] .

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All products are known compounds except for (E)-β-tolyl-seleno-p-methylstyrene, (E)-β-propylseleno-p-methoxy-styrene, (E)-β-propylseleno-p-chlorostyrene and (E)-β-heptylselenostyrene.
( E )-β-Tolylseleno- p -methylstyrene (Table 2, Entry 6).
Mp 35-36 °C; yield 91%. 1H NMR (400 MHz, CDCl3): δ = 7.43 (d, 2 H, J = 8.2 Hz), 7.20 (d, 2 H, J = 8.2 Hz), 7.81-7.12 (m, 4 H), 7.07 (d, 1 H, J = 15.6 Hz), 6.79 (d, 1 H, J = 15.6 Hz), 2.34 (s, 3 H), 2.31 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 137.42, 137.39, 132.94, 132.84, 130.01, 129.29, 125.88, 118.61, 21.18, 21.11. IR: ν = 3019, 2916, 2854, 1635, 1594, 1510, 1487, 1191, 1116, 1070, 1016, 962, 832, 805, 781 cm-1. Anal. Calcd for C16H16Se: C, 66.90; H, 5.61. Found: C, 66.91; H, 5.61.
( E )-β-Propylseleno- p -methoxystyrene (Table 2, Entry 8).
Viscous oil; yield 65%. 1H NMR (400 MHz, CDCl3): δ = 7.23 (d, 2 H, J = 8.8 Hz), 6.83 (d, 2 H, J = 8.8 Hz), 6.86 (d, 1 H, J = 16.0 Hz), 6.71 (d, 1 H, J = 16.0 Hz), 3.80 (s, 3 H), 2.77 (t, 2 H, J = 7.2 Hz), 1.73-1.82 (m, 2 H), 1.02 (t, 3 H, J = 7.2 Hz). 13C NMR (100 MHz, CDCl3): δ = 137.40, 131.94, 128.57, 127.00, 125.57, 119.44, 31.57, 30.30, 29.78, 28.76, 26.17, 22.58, 14.06. IR: ν = 3025, 2960, 1604, 1509, 1460, 1301, 1251, 1177, 1034, 947, 834, 776 cm-1. Anal. Calcd for C12H16OSe: C, 56.47; H, 6.32. Found: C, 56.44; H, 6.32.
( E )-β-Propylseleno- p -chlorostyrene (Table 2, Entry 10).
Viscous oil; yield 68%. 1H NMR (400 MHz, CDCl3): δ = 7.26 (d, 2 H, J = 8.2 Hz), 7.21 (d, 2 H, J = 8.2 Hz), 7.03 (d, 1 H, J = 16.4 Hz), 6.67 (d, 1 H, J = 16.4 Hz), 2.80 (t, 2 H, J = 7.4 Hz), 1.75-1.83 (m, 2 H), 1.04 (t, 3 H, J = 7.4 Hz). 13C NMR (100 MHz, CDCl3): δ = 136.84, 132.45, 130.32, 128.58, 126.67, 120.50, 28.28, 23.59, 14.39. IR: ν = 3021, 2961, 2928, 2869, 1597, 1570, 1494, 1444, 1376, 1281, 1214, 1028, 943, 730, 690 cm-1. Anal. Calcd for C11H13ClSe: C, 50.89; H, 5.05. Found: C, 50.84; H, 5.06.
( E )-β-Heptylselenostyrene (Table 2, Entry 11).
Viscous oil; yield 71%. 1H NMR (400 MHz, CDCl3): δ = 7.30 (d, 4 H, J = 4.0 Hz), 7.19-7.22 (m, 1 H), 7.05 (d, 1 H, J = 16.4 Hz), 6.73 (d, 1 H, J = 16.4 Hz), 2.82 (t, 2 H, J = 7.6 Hz), 1.72-1.80 (m, 2 H), 1.26-1.45 (m, 8 H), 0.88 (t, 3 H, J = 6.4 Hz). 13C NMR (100 MHz, CDCl3): δ = 137.40, 131.94, 128.57, 127.00, 125.57, 119.44, 31.57, 30.3, 29.78, 28.76, 26.17, 22.58, 14.06. IR: ν = 3022, 2956, 2925, 2854, 1652, 1597, 1570, 1494, 1460, 1221, 1182, 942, 729, 690 cm-1. Anal. Calcd for C15H22Se: C, 64.05; H, 7.88. Found: C, 64.01; H, 7.89.