Meng Huan, Jia Jun-Song, Yang Peng-Fei, Li Yu-Long, Yu Qiong, Shu Wei
Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Shenzhen Grubbs Institute, Guangming Advanced Research Institute, Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis Southern University of Science and Technology Shenzhen 518055 Guangdong P. R. China
College of Chemistry and Environmental Engineering, Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, Sichuan University of Science and Engineering Zigong 643000 P. R. China
Chem Sci. 2025 Jan 23;16(10):4442-4449. doi: 10.1039/d4sc07728h. eCollection 2025 Mar 5.
Catalytic methods by switching the least parameters for regioselective and site-divergent transformations to construct different architectures from identical and readily available starting materials are among the most ideal catalytic protocols. However, the associated challenge to precisely control both regioselectivity and site diversity renders this strategy appealing yet challenging. Herein, Ni-catalyzed cross-electrophile regioselective and site-divergent 1,2- and 1,3-arylalkylations of -acyl allylic amines have been developed. This Ni-catalyzed reductive three-component protocol enables 1,2-arylalkylation and 1,3-arylalkylation of allylic amines with aryl halides and alkyl halides with excellent chemo-, regio- and site-selectivity, representing the first example of controlled migratory difunctionalization of alkenes under reductive conditions. A wide range of terminal and internal unactivated allylic amines, aryl halides and alkyl precursors were tolerated, providing straightforward and efficient access to diverse C(sp)-rich branched aliphatic amines from identical starting materials.
通过切换最少参数进行区域选择性和位点发散性转化，以从相同且易于获得的起始原料构建不同结构的催化方法，是最理想的催化方案之一。然而，精确控制区域选择性和位点多样性这一相关挑战，使得该策略既具有吸引力又具有挑战性。在此，已开发出镍催化的酰基烯丙基胺的交叉亲电试剂区域选择性和位点发散性1,2 - 和1,3 - 芳基烷基化反应。这种镍催化的还原三组分反应方案能够使烯丙基胺与芳基卤化物和烷基卤化物进行1,2 - 芳基烷基化和1,3 - 芳基烷基化反应，具有出色的化学、区域和位点选择性，代表了还原条件下烯烃可控迁移双官能化的首个实例。该反应对多种末端和内部未活化的烯丙基胺、芳基卤化物和烷基前体具有耐受性，能从相同的起始原料直接有效地获得多种富含C(sp)的支链脂肪族胺。
