Pd-Catalyzed Asymmetric Amination of Enamines: Expedient Synthesis of Structurally Diverse N–C Atropisomers
Pd-Catalyzed Asymmetric Amination of Enamines: Expedient Synthesis of Structurally Diverse N–C Atropisomers
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DOI：
10.1021/acscatal.3c00732
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发表时间：
2023-05
期刊：
影响因子：
12.9
通讯作者：
P. Zhang;Changsheng Guo;Wang Yao;Chuan-Jun Lu;Yingzi Li;R. Paton;Ren-Rong Liu
中科院分区：
文献类型：
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作者：
P. Zhang;Changsheng Guo;Wang Yao;Chuan-Jun Lu;Yingzi Li;R. Paton;Ren-Rong Liu
过渡金属催化的烯胺的交叉偶联是一种有吸引力的制备具有N-C手性轴的化合物的方法;然而，它面临着相当大的挑战，仍然没有解决。在此，钯催化的胺化方法被开发用于构建结构不同的5 - 6联芳基和6 - 6非联芳基N-C阻转异构体。采用密度泛函理论对反应机理进行了解释，结果表明反应机理为Curtin-Hammett控制。N-C旋转发生沿着反应坐标，直到一个对映体决定的三中心还原消除过渡结构建立立体化学。该方法具有底物范围广、立体选择性高、催化体系简单、官能团耐受性好、动态动力学拆分等优点。
The transition-metal-catalyzed cross-coupling of enamines is an attractive method for producing compounds with an N–C chiral axis; however, it faces considerable challenges that remain unresolved. Herein, a palladium-catalyzed amination method was developed to construct structurally diverse five–six biaryl and six–six nonbiaryl N–C atropisomers. The reaction mechanism was explained using density functional theory calculations, which showed that the mechanism involved the Curtin–Hammett control. N–C rotation occurred along the reaction coordinate until an enantio-determining three-centered reductive elimination transition structure established the stereochemistry. The developed method is highly attractive because of its broad substrate scope, high stereoselectivity, simple catalytic system, good functional group tolerance, and dynamic kinetic resolution.