α,α'-双亚甲基锆杂环戊烷的构建及其在1,5-己二烯合成中的应用  

Preparation of α,α'-Bismethylenyl Zirconacyclopentane and Its Application in the Synthesis of 1,5-Hexadiene Derivatives

作　　者：胡麟峰[1] 王伟[1] 章彦婧[1] 林胜[1] 陆红燕[1] 郑卫新[1] 

机构地区：[1]杭州师范大学材料与化学化工学院,杭州310036

出　　处：《有机化学》2015年第3期662-671,共10页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.20972037);浙江省重点科技创新团队建设项目(No.2010R50017);杭州师范大学优秀中青年教师支持计划(No.HNUEYT-2011-01-013);教育部创新团队长江学者和创新团队发展计划(No.IRT1231)资助项目~~

摘　　要：锆杂环化合物因其多种反应活性而备受关注.2分子1,1-二取代联烯在低价锆物种"Cp2Zr(II)"作用下可发生分子间还原偶联形成α,α'-双亚甲基锆杂环戊烷,反应的区域及立体化学受到取代基空间效应影响显著.α,α'-双亚甲基锆杂环戊烷中含有两个sp2碳-金属键,与多种亲电试剂体系反应分别生成多种类型有机分子,可为2,5-二卤代-1,5-己二烯、具有1,5-二烯骨架的1,6-二羰基化合物等多功能有机分子提供新合成方法学.Zirconacycle has attached much attention owing to its various reactive behaviors. α,α＇-Bismethylenyl zirconacyclopentane could be prepared by reductive coupling reaction of two 1,1-disubstituted allenes promoted by low covalent zirconocene species ＂Cp2Zr（II）＂. The stereo- and regio-chemistry could be affected obviously by steric and electronic effect of the substituents in the allenes. Two sp2 carbon-metallic bonds in α,α＇-bismethylenyl zirconacyclopentane could be quenched by several electrophilic system and afford the novel methodologies for the synthesis of 1,1,6,6-tetrasubstituted 1,5-hexadiene, 2,5-dihalo-1,5-hexadiene and 1,6-dicarbonyl compound with the skeleton of 1,5-hexadiene.

关 键 词：α α'-双亚甲基锆杂环戊烷 1 5-己二烯 合成 选择性 

分 类 号：O623.122[理学—有机化学]