钯催化有机卤化物与烷基炔的Heck型反应  

Palladium Catalyzed Heck-Type Reaction of Organic Halides and Alkyl-Alkynes

作　　者：朱成浩 张俊良 Chenghao Zhu;Junliang Zhang(Department of Chemistry,Fudan University,Shanghai 200438,China)

机构地区：[1]复旦大学化学系,上海200438

出　　处：《化学进展》2020年第11期1745-1752,共8页Progress in Chemistry

基　　金：国家自然科学基金项目(No.21672067)资助。

摘　　要：烯烃的Heck反应经过几十年的发展已日趋成熟,但相应的钯催化有机卤化物与烷基炔的Heck反应生成联烯虽然有着原料简单易得的优点,但发展严重滞后。这一方面是由于活性中间体烯基钯自身难以发生β-H消除,导致其更容易发生质子化反应、碳卤化反应以及串联反应等竞争性反应,另一方面,联烯异构化以及非对称烷基炔的区域选择性问题同样限制了烷基炔Heck反应的研究进展。目前能高效促进烯基钯中间体β-H消除的方法主要有提高反应温度、芳基卤化合物引入取代基和改变配体等。本文主要叙述烷基炔的Heck反应过程中涉及到的烯基钯β-H消除生成联烯以及质子化反应、碳卤化反应和串联反应等竞争性反应,最后总结该反应存在的问题,并对其研究方向进行展望。As an important unit of molecular structure and organic building blocks,the development of new synthetic methods of allene has received much attention.The Heck and related cascade reaction of alkenes is arguably one of the most synthetically versatile method.However,the Heck reaction of alkyl-alkynes leading to allenes has lagged behind due to the energetically unfavoredβ-hydride elimination of vinyl palladium species.Several competitive reactions such as protonation,carbohalogenation and cascade reaction exist.Moreover,the isomerization of allene and the regioselectivity of unsymmetrical alkyl-alkynes also limited this research progress.To effectively promoteβ-hydride elimination of vinyl palladium species,several commonly-used strategies are the increasing reaction temperature,introduction of ortho-substituent to aryl halides and the development of ligand.In this mini-review,Heck and related reaction of alkyl-alkynes includingβ-hydride elimination reactions of vinyl palladium species,protonation reaction,carbohalogenation reaction,and cascade reaction are emphasized.Finally,the major limitation and an outlook this type of reaction are provided.

关 键 词：HECK反应 烷基炔烃 卤化物 联烯 轴手性 质子化 碳卤化 串联反应 

分 类 号：O623.12[理学—有机化学]