Formal[2+1]Cycloadditions of a Metallacyclopentadiene Unit with Alkynes:Constructing Tetracyclic Conjugated Frameworks with Bridgehead Metals  

作　　者：Zhenwei Chu Jinhua Li Dafa Chen Zhengyu Lu Weiran Meng Ming Luo Haiping Xia 

机构地区：[1]Shenzhen Grubbs Institute and Guangdong Provincial Key Laboratory of Catalysis,Department of Chemistry,Southern University of Science and Technology,Shenzhen,Guangdong 518055,China

出　　处：《Chinese Journal of Chemistry》2023年第16期1987-1993,共7页中国化学（英文版）

基　　金：the National Natural Science Foundation of China(Nos.21931002,22071098,22101115,and 22101123);the Shenzhen Science and Technology Innovation Committee(Nos.JCYJ20200109140812302 and JCYJ20210324105013035);the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)。

摘　　要：Comprehensive Summary Metallacyclopentadienes play a vital role in transition-metal mediated and catalyzed cycloaddition reactions of alkynes.Though versatile reactions of metallacyclopentadienes with alkynes have been disclosed,[2+1]cycloadditions of metallacyclopentadienes and alkynes have never been discovered.In present work,we report the formal[2+1]cycloadditions of a metallacyclopentadiene unit with a broad scope of commercial alkynes,providing a facile strategy to construct tetracyclic conjugated compounds.The deuterated experiment indicates a metal vinylidene intermediate has been involved in[2+1]cycloaddition.Moreover,the electrophilic substitution reaction of the tetracyclic conjugated compound with the aid of density functional theory(DFT)calculated Fukui functions is investigated.

关 键 词：METALLACYCLE CYCLOADDITION ALKYNES Electrophilic substitution CONJUGATION 

分 类 号：O62[理学—有机化学]