An unexpected palladium migration from vinylic sp^2 carbon to allylic sp^3 carbon  

作　　者：LI BiJie SHI ZhangJie 

机构地区：[1]Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Green Chemistry Center, Peking University, Beijing 100871 [2]China and State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

出　　处：《Chinese Science Bulletin》2010年第25期2807-2810,共4页

基　　金：supported by Peking University,the National Natural Science Foundation of China (20542001 and 20521202);the National Basic Research Program of China (2009CB825300)

摘　　要：A unique transformation to realize the allylic amination from vinylic bromides was described and an unexpected C-Pd migration was observed from sp2 carbon to adjacent allylic sp3 carbon initiated from vinyl bromide. Various 3-aryl-2-bromopropenes and secondary amines were surveyed and the allyl amination products were obtained in moderate isolated yields. The primary amine was not fit for this transformation. Mechanistic studies indicate that this migration went through β-hydride elimination and reverse C=C bond insertion.A unique transformation to realize the allylic amination from vinylic bromides was described and an unexpectecl C-Pd migranon was observed from sp2 carbon to adjacent allylic sp3 carbon initiated from vinyl bromide. Various 3-aryl-2-bromopropenes and secondary amines were surveyed and the allyl arnination products were obtained in moderate isolated yields. The primary amine was not fit for this transformation. Mechanistic studies indicate that this migration went through β-hydride elimination and reverse C=C bond insertion.

关 键 词：SP3 SP2 碳烯 迁移 钯 烯丙基 溴乙烯 乙烯基 

分 类 号：TQ655[化学工程—精细化工] TP316.7[自动化与计算机技术—计算机软件与理论]