Alkenylzirconocene-mediated preparation of alkenylphosphines
Alkenylzirconocene-mediated preparation of alkenylphosphines
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DOI：
10.1021/jo071089v
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发表时间：
2007-11-09
影响因子：
3.6
通讯作者：
Takahashi, Tamotsu
中科院分区：
文献类型：
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作者：
Miyaji, Taichi;Xi, Zhenfeng;Takahashi, Tamotsu
通过烯基锆茂与氯膦的反应制备了具有各种取代基的烯基膦。（α - 未取代烯基）锆茂与Ph₂PCl或PhPCl₂反应以良好的产率得到相应的烯基膦。另一方面，（α - 未取代烯基）锆茂与Pr₂PCl的直接反应无法进行。类似地，（α - 取代烯基）锆茂也不能直接与氯膦反应。然而，在CuCl存在下这些反应能够进行，得到相应的作为CuCl配合物的烯基膦。用Na₂(dtc)（dtc = N,N - 二乙基二硫代氨基甲酸酯）或Na₄(edta)处理铜配合物可使烯基膦从铜中心游离出来。整个方案可适用于通过烯基锆茂物种从炔烃制备各种烯基膦。
Alkenylphosphines with various substituents were prepared by the reaction of an. alkenylzirconocene with a chlorophosphine. Reactions of (alpha-unsubstituted alkenyl)zirconocenes with Ph2PCl or PhPCl2 gave the corresponding alkenylphosphines in good yields. On the other hand, direct reactions of (a-unsubstituted alkenyl)zirconocenes with Pr2PCl did not proceed. Analogously, (a-substituted alkenyl)zirconocenes did not react with chlorophosphines directly. However, these reactions proceeded in the presence of CuCl affording the corresponding alkenylphosphines as CuCl complexes. Treatment of the copper complexes with Na-2(dtc) (dtc = N,N-diethyldithiocarbamate) or Na4(edta) liberated free alkenylphosphines from the copper centers. The overall protocol could be applicable to preparation of a variety of alkenylphosphines from alkynes via alkenylzirconocene species.