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Transition-metal free C–N bond formation from alkyl iodides and diazonium salts via halogen-atom transfer
Nature Communications ( IF 14.7 ) Pub Date : 2022-12-27 , DOI: 10.1038/s41467-022-35613-7
Jing Zhang 1 , Min Jiang 1 , Chang-Sheng Wang 2 , Kai Guo 2 , Quan-Xin Li 3 , Cheng Ma 3 , Shao-Fei Ni 3 , Gen-Qiang Chen 4 , Yan Zong 4 , Hua Lu 1 , Li-Wen Xu 1 , Xinxin Shao 1
Affiliation  

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.



中文翻译:


通过卤素原子转移从烷基碘和重氮盐形成无过渡金属的 C-N 键



由于胺在药物、材料和农用化学品中的普遍应用,CN键的构建仍然是有机化学中最重要目标的一部分。然而,通过经典的 S N 2 取代烷基卤来消除 E2 会导致产生作为主要副产物的烯烃。因此,特别是在叔碳中心上形成具有挑战性的C(sp 3 )-N键仍然是非常理想的。在此,我们提出了一种在烷基碘和易于获得的重氮盐之间高效制备伯、仲和叔烷基胺的实用替代方案。这种稳健的转变仅在无过渡金属的反应条件下采用Cs 2 CO 3促进卤素原子转移(XAT)过程,从而提供了一种快速组装不同C(sp 3 )-N键的方法。此外,重氮盐在反应中充当烷基自由基引发剂和胺化试剂。机理研究表明,该反应通过卤素原子转移过程产生活性烷基自由基,与重氮阳离子偶联形成最终产物。

更新日期:2022-12-28
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