Zirconacycle-mediated synthesis of carbocycles  

作　　者：CHEN Chao XI ChanJuan 

机构地区：[1]Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry,Tsinghua University, Beijing 100084, China

出　　处：《Chinese Science Bulletin》2010年第29期3235-3247,共13页

基　　金：supported by the National Natural Science Foundation of China (20172032, 20872076);the Doctoral Program of Higher Education (200800030072)

摘　　要：Direct transformation of five-membered zirconacycles to carbocyclic compounds is of great synthetic interest.The reaction of zirconacycles with electrophiles containing at least two reactive functional groups or an oxidant affords various carbocycles through cross coupling,addition,and/or oxidative coupling reactions.In this paper,we present our recent results on the zirconacycle-mediated formation of carbocycles,including:(1) 1,1-cycloaddition of oxalyl dichloride with zirconacycles;(2) benzoquinone-promoted coupling of zirconacyclopentadienes in the presence of CuCl;(3) cycloaddition of zirconacyclopentadienes to quinones;(4) cycloaddition of zirconacyclopentadiene with 2-bromoacrylate,2-bromoacrylaldehyde and 3-bromofuran-2,5-dione in the presence of CuCl;(5) one-pot coupling of two alkynes and an alkene to form cyclohexene derivatives via zirconacyclopentadienes;and(6) dianionic cycloaddition of decatetraenes with esters or acyl chlorides to form nine-membered carbocycles.Direct transformation of five-membered zirconacycles to carbocyclic compounds is of great synthetic interest. The reaction of zirconacycles with electrophiles containing at least two reactive functional groups or an oxidant affords various carbocycles through cross coupling, addition, and/or oxidative coupling reactions. In this paper, we present our recent results on the zirconacycle-mediated formation of carbocycles, including： （1） 1,1-cycloaddition of oxalyl dichloride with zirconacycles; （2） benzoquinone-promoted coupling of zirconacyclopentadienes in the presence of CuC1; （3） cycloaddition of zirconacyclopentadienes to quinones; （4） cycloaddition of zirconacyclopentadiene with 2-bromoacrylate, 2-bromoacrylaldehyde and 3-bromofuran-2,5-dione in the presence of CuCl; （5） one-pot coupling of two alkynes and an alkene to form cyclohexene derivatives via zirconacyclopentadienes; and （6） dianionic cycloaddition of decatetraenes with esters or acyl chlorides to form nine-membered carbocycles.

关 键 词：碳环化合物 介导 氧化偶联反应 合成 交叉耦合 环加成 氧化剂 官能团 

分 类 号：O624[理学—有机化学] S511.03[理学—化学]