Redox-neutral ipso/ortho alkenylcyanation of(hetero)arylboronic acid enabled by 1,4-rhodium migration and fragmentation  

作　　者：Chenxia Guo Donghui Xing Huanfeng Jiang Liangbin Huang 

机构地区：[1]The State Key Laboratory of Pulp and Paper Engineering,School of Chemistry and Chemical Engineering,Key Laboratory of Functional Molecular Engineering of Guangdong Province,South China University of Technology,Guangzhou,510640,China

出　　处：《Science China Chemistry》2023年第8期2283-2291,共9页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21971074);the Natural Science Foundation of Guangdong Province(2022A1515010660,2021A1515220024);Natural Science Foundation of Guang Zhou(202102020982)。

摘　　要：A mild,chemoselective,redox-neutral ipso/ortho alkenylcyanation of arylboronic acids with homopropargylic malononitriles via 1,4-rhodium migration and fragmentation is reported.A variety of 2-vinyl arylnitriles are obtained in good yields(51examples,ava.69%yields)through this strategy,which is characterized by its broad substrate scope,great functional group tolerance,and mild conditions.Mechanism studies indicate that the fragmentation is temperature dependent.The primary asymmetric exploration for the non-fragmentation product already shows promising results.The separation of the two cyano groups of homopropargylic malononitriles results in the formation of aromatic nitrile and aliphatic nitrile in one molecule,which enables the further transformations of the products.

关 键 词：1 4-rhodium migration alkenylcyanation cyano transfer malononitriles 

分 类 号：O621.25[理学—有机化学]