镍/双咪唑催化的芳基氮丙啶与芳基碘化物的电化学对映选择性还原交叉偶联。

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, CAS, Shanghai, China.

Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva, 841051, Israel.

Nat Commun. 2023 Apr 22;14(1):2322. doi: 10.1038/s41467-023-37965-0.

Here, we report an asymmetric electrochemical organonickel-catalyzed reductive cross-coupling of aryl aziridines with aryl iodides in an undivided cell, affording β-phenethylamines in good to excellent enantioselectivity with broad functional group tolerance. The combination of cyclic voltammetry analysis of the catalyst reduction potential as well as an electrode potential study provides a convenient route for reaction optimization. Overall, the high efficiency of this method is credited to the electroreduction-mediated turnover of the nickel catalyst instead of a metal reductant-mediated turnover. Mechanistic studies suggest a radical pathway is involved in the ring opening of aziridines. The statistical analysis serves to compare the different design requirements for photochemically and electrochemically mediated reactions under this type of mechanistic manifold.

在这里，我们报告了一种不对称电化学有机镍催化的未分割电池中芳基氮丙啶与芳基碘化物的还原交叉偶联反应，在广泛的官能团容忍度下，以良好到优异的对映选择性得到β-苯乙胺。催化剂还原电位的循环伏安分析以及电极电位研究的结合为反应优化提供了一种便捷的途径。总的来说，这种方法的高效率归因于镍催化剂的电还原介导的转化，而不是金属还原剂介导的转化。机理研究表明，氮丙啶的开环涉及自由基途径。统计分析用于比较在这种机理类型下光化学和电化学介导反应的不同设计要求。