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LETTER
Table 3 Reuse of CuI–IL Reaction System
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Cyclea Product
Yield
(%)c
Cycle
Product
(Z:E)
Yield
(%)
(Z:E)b
1
2
98:2
98:2
90
89
3
4
98:2
98:2
84
85d
a Reaction conditions: CuI (10 mol%), (Z)-b-bromostyrene (1 mmol),
thiolphenol (1.1 mmol) in IL 2 (2.4 g) at 90 °C.
b The ratio was based on the 1H NMR spectrum (CH=CH).
c Isolated yield based on (Z)-b-bromostyrene.
d Yield of the reaction after the IL–CuI system was treated with
K2CO3 in acetone.
In summary, we have developed a mild, efficient and
comparatively cheap methodology for the synthesis of
(Z)-vinyl chalcogenides by coupling vinyl bromides with
thiols or diphenyl diselenide in a highly stereoselective
manner using CuI as catalyst. The reaction was conducted
only in ionic liquids and no base or other additives were
needed. The best results were obtained in the ionic liquid
based on N,N-dimethylglycine with the retention of ste-
reochemistry. The ionic liquid 2 played multiple roles in
this reaction system, such as a high polar solvent to im-
prove the reaction yield, an excellent promoter for the
copper(I)-catalyzed coupling reaction, and a based to
neutralize the by-product HBr. Additionally, the reaction
avoided the use of palladium and/or expensive additives
and vinyl iodides.
(11) Bates, C. G.; Saejueng, P.; Doherty, M. Q.; Venkataraman,
D. Org. Lett. 2004, 6, 5005.
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(14) Luo, Y.; Wu, J. X.; Ren, R. X. Synlett 2003, 1734.
(15) Li, S.; Lin, Y.; Xie, H.; Zhang, S.; Xu, J. Org. Lett. 2006, 8,
391; and ref. 8 cited therein.
Acknowledgment
This work was financially supported by the Natural Science Foun-
dation of China (No. 20372058).
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