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Synlett 2003(13): 2080-2082  
DOI: 10.1055/s-2003-41480
LETTER
© Georg Thieme Verlag Stuttgart · New York

CuX2-Mediated Halogenation of Alkylidenecyclopropanes: A Highly Efficient and Stereoselective Method for the Preparation of Z-2, 4-Dihalobutenes

Hongwei Zhoua, Xian Huang*a,b, Wanli Chena
a Department of Chemistry, Zhejiang University (Campus Xixi), Hangzhou 310028, P. R. China
b State Key Laboratory of Oganometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China
e-Mail: huangx@mail.hz.zj.cn;
Further Information

Publication History

Received 8 July 2003
Publication Date:
08 October 2003 (online)

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Abstract

A convenient and efficient method for the synthesis of (Z)-2,4-dihalobutenes, a useful building block in organic synthesis, was reported in good yield by the reaction of alkylidenecyclopropane­s and CuX2 (or CuI/I2).

Key words

copper-mediated - halogenation - alkylidenecyclo­propane - stereoselective - (Z)-2,4-dihalobutene

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7

General Procedure for the Synthesis of 2: Condition A:
A solution of 1a (130 mg, 1.0 mmol) with CuBr2 (450 mg, 2.0 mmol) in 5 mL of CH3CN was stirred at 65 °C for 14 h. The mixture was then diluted with 30 mL of sat. NH4Cl and extracted three times with n-hexane. The organic phases were combined and dried over MgSO4. After evaporation, the residues were purified via chromatography on silica gel with n-hexane as the eluent to afford 254 mg (82%) of 2a. Condition B. A solution of 1a (130 mg, 1.0 mmol) with I2 (510 mg, 2.0 mmol) and CuI (20 mg, 0.1 mmol) in 10 mL of CH3CN was stirred at 65 °C for 16 h. The mixture was then diluted with 30 mL of sat. Na2S2O3 and extracted three times with n-hexane. The organic phases were combined and dried over MgSO4. After evaporation, the residues were purified via chromatography on silica gel with n-hexane as the eluent to afford 349 mg (91%) of 2c.

8

Selected Data of Compounds 2c and 2g: (a)Spectral and analytical data for 2c: IR(neat): 1491 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.48-7.46 (m, 2 H), 7.37-7.31 (m, 3 H), 6.80 (s, 1 H), 3.41-3.38 (t, J = 7.0 Hz, 2 H), 3.16-3.12 (t, J = 7.0 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 137.9, 136.9, 128.6, 128.2, 128.1, 105.0, 49.9, 5.18. MS (EI): m/z (%) = 384 (21.41) [M+], 257 (12.16), 130(100). Anal. Calcd for C10H10I2: C, 31.28; H, 2.62. Found: C, 31.55; H, 2.39.
(b)Spectral and analytical data for 2g: IR(neat): 1504 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.36-7.32 (m, 52 H), 7.28-7.21 (m, 3 H), 3.80& ndash;3.77 (t, J = 6.8 Hz, 2 H), 2.98-2.95 (t, J = 6.8 Hz, 2 H), 2.09 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 142.5, 135.5, 128.6, 128.3, 127.4, 125.7, 42.4, 39.0. MS (EI): m/z (%) = 217 (1.98) [M+ + 3], 216 (16.67) [M+ + 2], 215 (3.93) [M+ + 1], 214 (25.64) [M+], 129(100). Anal Calcd for C11H12Cl2: C, 61.42; H, 5.62. Found: C, 61.71; H, 5.88.