Transition-metal free C–N bond formation from alkyl iodides and diazonium salts via halogen-atom transfer

Nature Communications

Article

Yan Zong¹  Gen-Qiang Chen¹  Chang-Sheng Wang²  Kai Guo²  Li-Wen Xu³  Min Jiang³  Hua Lu³  Xinxin Shao³  Jing Zhang³  Shao-Fei Ni⁴  Quan-Xin Li⁴  Cheng Ma⁴ 

[1] Academy for Advanced Interdisciplinary Studies and Department of Chemistry, Southern University of Science and Technology, 1088 Xueyuan Road, 518055, Shenzhen, China;College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, 30 Puzhu Rd S, 211816, Nanjing, China;College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, China;Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guang-dong Province, Shantou University, 515063, Shantou, Guangdong, China;

DOI  :  10.1038/s41467-022-35613-7

 received in 2022-06-15, accepted in 2022-12-13,  发布年份 2022

来源: Springer

【 摘 要 】

Construction of C-N bond continues to be one part of the most significant goals in organic chemistry because of the universal applications of amines in pharmaceuticals, materials and agrochemicals. However, E2 elimination through classic SN2 substitution of alkyl halides lead to generation of alkenes as major side-products. Thus, formation of a challenging C(sp3)-N bond especially on tertiary carbon center remains highly desirable. Herein, we present a practical alternative to prepare primary, secondary and tertiary alkyl amines with high efficiency between alkyl iodides and easily accessible diazonium salts. This robust transformation only employs Cs2CO3 promoting halogen-atom transfer (XAT) process under transition-metal-free reaction conditions, thus providing a rapid method to assemble diverse C(sp3)-N bonds. Moreover, diazonium salts served as alkyl radical initiator and amination reagent in the reaction. Mechanism studies suggest this reaction undergo through halogen-atom transfer process to generate active alkyl radical which couples with diazonium cations to furnish final products.

【 授权许可】

CC BY   
© The Author(s) 2022

【 图 表 】

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