Zirconium-mediated cross-coupling of terminal alkynes and vinyl bromides:: Selective synthesis of cyclobutene and 1,3-diene derivatives
Zirconium-mediated cross-coupling of terminal alkynes and vinyl bromides:: Selective synthesis of cyclobutene and 1,3-diene derivatives
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DOI：
10.1002/chem.200305337
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发表时间：
2004-01-05
影响因子：
4.3
通讯作者：
Fañanás, FJ
中科院分区：
文献类型：
--
作者：
Barluenga, J;Rodríguez, F;Fañanás, FJ
本文报道了在锆催化下烯基锂化合物与溴代乙烯非对映选择性合成1，3-丁二烯或环丁烯衍生物。关键步骤包括从卤代烯烃生成茂锆-炔配合物，然后与溴代烯基偶联。因此，形式上该方法假定末端炔和烯基溴之间的交叉偶联反应。此外，使用丁基乙烯基醚代替溴乙烯基作为不饱和体系允许替代地获得不同的1，3-丁二烯区域异构体。
A diastereoselective synthesis of 1,3-butadiene or cyclobutene derivatives by a zirconium-mediated reaction of alkenyllithium compounds and vinyl bromides is reported. The key steps involve the generation of zirconocene-alkyne complexes from haloalkenes and subsequent coupling with alkenyl bromides. Thus, formally the process supposes the cross-coupling reaction between a terminal alkyne and an alkenyl bromide. Moreover, the use of butyl vinyl ether instead of vinyl bromide as the unsaturated system allows an alternative access to different 1,3-butadiene regioisomers.