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DOI: 10.1055/s-2008-1077955
CuI-Catalyzed Cross-Coupling Reaction of (E)-Vinyl Bromides with Nitrogen-Containing Heterocycles
Publication History
Publication Date:
15 July 2008 (online)
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
- Supporting Information for this article is available online:
- Supporting Information
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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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References and Notes
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.
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.