Pd-Catalyzed Asymmetric Amination of Enamines: Expedient Synthesis of Structurally Diverse N–C Atropisomers,ACS Catalysis

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Pd-Catalyzed Asymmetric Amination of Enamines: Expedient Synthesis of Structurally Diverse N–C Atropisomers
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-05-23 , DOI: 10.1021/acscatal.3c00732
Peng Zhang ₁ , Chang-Qiu Guo ₁ , Wang Yao ₁ , Chuan-Jun Lu ₁ , Yingzi Li ₂ , Robert S. Paton ₂ , Ren-Rong Liu ₁

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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.

中文翻译：

Pd 催化的烯胺不对称胺化：结构多样的 N-C 阻转异构体的便捷合成

过渡金属催化的烯胺交叉偶联是制备具有 N-C 手性轴的化合物的一种有吸引力的方法；然而，它面临着尚未解决的相当大的挑战。在此，开发了一种钯催化的胺化方法来构建结构多样的五六联芳基和六六非联芳基 N-C 阻转异构体。使用密度泛函理论计算解释了反应机理，表明该机理涉及 Curtin-Hammett 控制。N-C 旋转沿反应坐标发生，直到对映体确定的三中心还原消除过渡结构建立立体化学。该方法具有广泛的底物范围、高立体选择性、简单的催化体系、良好的官能团耐受性等优点，极具吸引力，

更新日期：2023-05-23

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