Liu Xiaochen, Hee Samual, Sapir Netanel G, Li Alvin, Farkruzzaman Syed, Liu Jianbo, Chen Yu
Department of Chemistry and Biochemistry, Queens College of the City University of New York, 65-30 Kissena Blvd., Queens, New York, 11367, United States.
Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, 365 Fifth Ave., New York, New York 10016, United States.
European J Org Chem. 2024 Jun 17;27(23). doi: 10.1002/ejoc.202400067. Epub 2024 Apr 10.
-BuNI/KSO mediated C-N coupling between aldehydes and amides is reported. A strong electronic effect is observed on the aromatic aldehyde substrates. The transformylation from aldehyde to amide takes place exclusively when an aromatic aldehyde bears electron-donating groups at either the or position of the formyl group, while the cross-dehydrogenative coupling dominates in the absence of these groups. Both the density functional theory (DFT) thermochemistry calculations and experimental data support the proposed single electron transfer mechanism with the formation of an acyl radical intermediate in the cross-dehydrogenative coupling. The -BuNI/KSO mediated oxidative cyclization between 2-aminobenzamide and aldehydes is also reported, with four quinazolin-4(3)-ones prepared in 65-99% yields.
报道了叔丁基异腈/硫酸钾介导的醛与酰胺之间的C-N偶联反应。在芳香醛底物上观察到强烈的电子效应。当芳香醛在甲酰基的邻位或对位带有供电子基团时，醛向酰胺的甲酰化反应会专一发生，而在没有这些基团时，交叉脱氢偶联反应占主导。密度泛函理论（DFT）热化学计算和实验数据均支持所提出的单电子转移机制，即在交叉脱氢偶联反应中形成酰基自由基中间体。还报道了叔丁基异腈/硫酸钾介导的2-氨基苯甲酰胺与醛之间的氧化环化反应，制备得到了4种喹唑啉-4(3)-酮，产率为65-99%。
