一种制备7-氮杂-1-磷杂降冰片烷配合物的方法：1-亚胺基磷杂环丙烷配合物的应变促进重排及与烯烃的环加成反应。
An approach to 7-aza-1-phosphanorbornane complexes: strain promoted rearrangement of 1-iminylphosphirane complexes and cycloaddition with olefins.
作者信息
Xu Yang, Wang Min, Wei Donghui, Tian Rongqiang, Duan Zheng, Mathey François
机构信息
College of Chemistry and Molecular Engineering, International Phosphorus Laboratory, International Joint Research Laboratory for Functional Organophosphorus Materials of Henan Province, Zhengzhou University, Zhengzhou 450001, P. R. China.
出版信息
Dalton Trans. 2019 Apr 23;48(17):5523-5526. doi: 10.1039/c9dt00838a.
1-Iminylphosphirane W(CO)5 complexes react with alkenes under an atmosphere of CO at 130 °C to form the original 7-aza-1-phosphanorbornane complexes. The reaction works well with both electron-rich and electron-poor alkenes. On the basis of DFT calculations, we propose a mechanism including the rearrangement of phosphirane into a dipolar five-membered ring and the following cycloaddition of this dipolar intermediate with alkenes.
1-亚氨基膦杂环丙烷W(CO)5配合物在130℃的CO气氛下与烯烃反应，形成原来的7-氮杂-1-磷杂降冰片烷配合物。该反应对富电子烯烃和缺电子烯烃都适用。基于密度泛函理论计算，我们提出了一种机理，包括膦杂环丙烷重排为偶极五元环以及该偶极中间体随后与烯烃的环加成反应。
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