Acceptorless dehydrogenative amination of alkenes for the synthesis of N-heterocycles

作     者：Jia-Lin Tu Wan Tang Shi-Hui He Ma Su Feng Liu Jia-Lin Tu;Wan Tang;Shi-Hui He;Ma Su;Feng Liu

作者机构：Jiangsu Key Laboratory of Neuropsychiatric Diseases and Department of Medicinal ChemistryCollege of Pharmaceutical SciencesSoochow UniversitySuzhou 215123China Key Laboratory of Organofluorine ChemistryShanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2022年第65卷第7期

页      面：1330-1337页

核心收录：

学科分类：07[理学] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (18KJA350001) the Priority Academic Program Development of the Jiangsu Higher Education Institutes (PAPD)。 

主　　题：nitrogen-centered radical alkene amination photoredox cyclization N-heterocycle 

摘      要：Catalytic amination of alkenes is one of the most attractive reactions for the construction of complex heterocycles with nitrogen centers. Herein, we present that synergistic photoredox and cobaloxime catalysis allows for highly efficient and mild dehydrogenative reactions between various NH nucleophiles and di-, tri-, and tetrasubstituted alkenes in the absence of external oxidants, thus enabling access to an array of N-heterocycles. Notably, both Z-and E-alkene-containing N-heterocycles are accessible. Mechanistic studies indicated that the Z-cinnamyl derivatives could be generated by photocatalytic E to Z alkene isomerization through an energy transfer process. Moreover, we find that sluggish energy transfer could inhibit the E to Z alkene isomerization process, thus offering the cinnamyl derivatives with E-selectivity. Our results highlight the benefits of the reactions using dual photoredox and cobaloxime catalysis to lead to diverse N-heterocycles.