Manganese-Catalyzed Anti-Markovnikov Hydroarylation of Enamides:Modular Synthesis of Arylethylamines  

作　　者：Yjie He Chaoyu Du Jian Han Jie Han Chengjian Zhu Jin Xie 

机构地区：[1]State Key Laboratory of Coordination Chemistry Jiangsu Key Laboratory of Advanced Organic Materials,Chemistry and Biomedicine Innovation Center(ChemBIC),School of Chemistry and Chemical Engineering,Nanjing University,Nanjing,Jiangsu 210023,China [2]Green Catalysis Center,College of Chemistry and Molecular Engineering,Zhengzhou University,Zhengzhou,Henan 45000i,China [3]Advanced Catalytic Engineering Research Center of the Ministry of Education,Hunan University,Changsha,Hunan 410082,China

出　　处：《Chinese Journal of Chemistry》2022年第13期1546-1552,共7页中国化学（英文版）

基　　金：We gratefully acknowledge the National Natural Science Foundation of China(22122103,22101130,22001116,21971108,21971111,21732003);the National Key Research and Development Program of China(2021YFC2101901);the Fundamental Research Funds for the Central Universities(020514380252);the Natural Science Foundation of Jiangsu Province(Grant No.BK20190006);the Guangdong Basic and Applied Basic Research Foundation(2020A1515110816);the"Innovation&Entrepreneurship Talents Plan"of Jiangsu Province.Nian Li,Chuan-Gang Zhao,Junheng Liu are warmly acknowledged to reproduce experimental procedures for products 3ii,5p and 3a.

摘　　要：The arylethylamine framework is a prevalent motif in a great range of biologically important organic compounds.One intractable task for frontline drug discovery is to find structurally new medicine candidates instead of opioid,based on the construction of a rich chemical space of arylethylamine motif In this report,a practical protocol for the synthesis of arylethylamine functionality common in pharmaceutical chemicals has been developed.It proceeds by Mn-catalyzed anti-Markovnikov hydroarylation of electron-rich enamides under mild conditions without the use of ligands.In spite of mismatched electronic effects during the manganese-mediated migratory insertion process,both terminal and internal enamides can be regioselectively hydroarylated with various aryl boronic acids in 15 min.Also,the successful hydroalkenylation of enamides with alkenyl boronic acids in air atmosphere affords an elegant route to synthetically useful β-alkenylated amines in satisfactory yields.The synthetic robustness and practicality of the reaction reveal its simple operation,short reaction time,viability on a gram-scale and its value in late-stage modification of complex molecules.

关 键 词：ALKENES ANTI-MARKOVNIKOV Homogeneous catalysis AMINES Difunctionalization 

分 类 号：O62[理学—有机化学]