| 炔的金属烯丙化反应的研究 |
| |
| 引用本文： | 魏运洋,E.Negishi.炔的金属烯丙化反应的研究[J].南京理工大学学报(自然科学版),1989(1). |
| |
| 作者姓名： | 魏运洋 E.Negishi |
| |
| 作者单位： | 华东工学院化工学院
(魏运洋)，美国Purdue大学(E.Negishi) |
| |
| 摘 要： | 在有机锆络合物(Cp_2ZrCl_2)存在下,取代烯丙基二甲基铝(A,B)可与一烷基或二烷基取代的炔烃发生加成反应。用盐酸处理加成中间体,生成1,4-戊二烯衍生物(1,2)、反应具有很高的立体选择性,几乎100%为同向加成,不发生烯丙基重排。取代烯丙基氯化锌(C,D)在无过渡金属络合物存在下,与炔烃发生加成反应,反应中,伴随完全的烯丙基重排。根据实验结果,对以上两类金属烯丙化反应的机理进行了讨论。
|
| 关 键 词： | 有机金属反应[34AG] 反应机理[34AF] 烯丙基重排[34AG] 锆络合物[34F] 反应选择性 |
Study on Allylmetallation of Alkynes |
| |
| Wei Yunyang,E. Negishi.Study on Allylmetallation of Alkynes[J].Journal of Nanjing University of Science and Technology(Nature Science),1989(1). |
| |
| Authors: | Wei Yunyang E Negishi |
| |
| Institution: | Wei Yunyang;E. Negishi |
| |
| Abstract: | It was found that substituted allylaluminiumreagents(A, B) add to both terminal and nonterminal alkynes inthe presence of zirconium complex(Cp_2ZrCl_2). Treatment of theinitially formed intermediates with an acid gives Various kindsof pentadiene derivatives(1. 2). The reactions are highly ster-eoselective and proceed exclusively by sny-addition withoutallylic rearrangement. Substituted allylzinc ?reagents?(C, D) add to functionalizedalkynes without the presence of any kinds of transition metalcomplexes. The reactions proceed with clean allylic rearrange-ment. The mechanismic aspects of the two allylmetallation reac-tions are discussed according to the experimental observations. |
| |
| Keywords: | Organometallic reaction Reaction mechanism Allylic rear rangement Zirconium compound Reaction selectivity |
| 本文献已被 CNKI 等数据库收录！ |
|
