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Synlett 2008(13): 2011-2016  
DOI: 10.1055/s-2008-1077955
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

CuI-Catalyzed Cross-Coupling Reaction of (E)-Vinyl Bromides with Nitrogen-Containing Heterocycles

Jincheng Mao*a, Qiongqiong Huab, Jun Guoa, Daqing Shia,b, Shunjun Jia
a Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215123, P. R. of China
Fax: +86(512)65880089; e-Mail: jcmao@suda.edu.cn;
b Department of Chemistry, Xuzhou Normal University, Xuzhou 221116, P. R. of China
Further Information

Publication History

Received 18 April 2008
Publication Date:
15 July 2008 (online)

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Abstract

An efficient and straightforward copper-catalyzed method allowing vinylation of N-nucleophiles with various substituted (E)-vinyl bromides under palladium-free and ligand-free conditions has taken a high yield (up to 95%). Noteworthy is that the double-bond geometry of these vinyl halides was retained with our protocol.

Key words

halides - nucleophiles - copper - cross-coupling - heterocycles

    References and Notes

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    Colorless oil. ¹H NMR (CDCl3): δ = 7.68 (d, J = 7.2 Hz, 1 H, ArH), 7.30-7.40 (m, 3 H, ArH), 7.06 (d, J = 8.0 Hz, 1 H, CH=CHPh), 6.42 (d, J = 8.0 Hz, 1 H, CH=CHPh).

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25

General Procedure for C-N Coupling Reactions of β-Bromostyrene and Heterocycle Copper(I) iodide (0.1 equiv) and Cs2CO3 (2.0 equiv) were added to a screw-capped test tube. The tube was then evacuated and backfilled with argon (3 cycles). N,N-Dimethylformamide (2 mL), nitrogen-containing heterocycles (1.2 equiv; if liquid) and vinyl halide (1.0 equiv; if liquid) were added by syringe at r.t. The tube was again evacuated and backfilled with argon (3 cycles). The mixture was heated to 120 ˚C and stirred for 36-50 h. After cooling to r.t., the mixture was diluted with H2O, and the combined aqueous phases were extracted three times with EtOAc. The organic layers were combined, dried over Na2SO4, and concentrated to yield the crude product, which was further purified by silica gel chromatography, using PE and EtOAc as eluents to provide the desired product.
Characteristic Data of Representative Products Compound 1:²¹,²² 95%; mp 184-185 ˚C. ¹H NMR (DMSO-d 6): δ = 8.02 (s, 1 H, 2-H in imidazole), 7.85 (d, J = 14.4 Hz, 1 H, CH=CHPh), 7.71 (s, 1 H, ArH), 7.26-7.51 (m, 5 H, ArH), 7.05 (s, 1 H, ArH), 7.01-7.05 (m, 2 H, CH=CHPh and ArH). ¹³C NMR (CDCl3): δ = 136.1, 134.8, 130.8, 129.4, 128.5, 126.6, 123.1, 119.3, 116.7. HRMS: m/z calcd for C11H10N2 [M+ + H]: 170.0844; found: 170.0843.
Compound 12: 91%; mp 78-80 ˚C. ¹H NMR (CDCl3): δ = 7.63 (d, J = 8.0 Hz, 2 H, in ArH), 7.49-7.58 (m, 3 H, in CH=CHPh and ArH), 7.39 (d, J = 8.8 Hz, 2 H, ArH), 7.15-7.30 (m, 2 H, ArH), 6.91 (d, J = 8.8 Hz, 2 H, ArH), 6.64-6.68 (m, 2 H, CH=CHPh and ArH), 3.84 (s, 3 H, CH3O). ¹³C NMR (CDCl3): δ = 159.2, 136.0, 129.5, 129.0, 127.3, 124.3, 123.0, 122.4, 121.6, 121.2, 114. 7, 110.0, 105.3, 55.7. HRMS: m/z calcd for C17H15NO [M+ + H]: 249.1154; found: 249.1153.

28

Colorless oil. ¹H NMR (CDCl3): δ = 7.48 (s, 1 H, ArH), 7.27-7.29 (m, 3 H, ArH), 7.09-7.12 (m, 2 H, ArH), 7.04 (s, 1 H, ArH), 6.86 (s, 1 H, ArH), 6.74 (d, J = 9.2 Hz, 1 H, CH=CHPh), 6.36 (d, J = 9.2 Hz, 1 H, CH=CHPh). ¹³C NMR (CDCl3): δ = 137.4, 134.1, 130.0, 129.1, 128.9, 128.7, 123.8, 122.8, 118.9.