Liu Xixi, Huang Liang, Ma Yuandie, She Guoqiang, Zhou Peng, Zhu Liangfang, Zhang Zehui
Key Laboratory of Catalysis and Materials Sciences of the Ministry of Education, South-Central Minzu University, Wuhan, China.
Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan, China.
Nat Commun. 2024 Aug 15;15(1):7012. doi: 10.1038/s41467-024-51307-8.
A single-atom catalyst with generally regarded inert Zn-N motifs derived from ZIF-8 is unexpectedly efficient for the activation of alcohols, enabling alcohol-mediated alkylation and transfer hydrogenation. C-alkylation of nitriles, ketones, alcohols, N-heterocycles, amides, keto acids, and esters, and N-alkylation of amines and amides all go smoothly with the developed method. Taking the α-alkylation of nitriles with alcohols as an example, the α-alkylation starts from the (1) nitrogen-doped carbon support catalyzed dehydrogenation of alcohols into aldehydes, which further condensed with nitriles to give vinyl nitriles, followed by (2) transfer hydrogenation of C=C bonds in vinyl nitriles on Zn-N sites. The experimental results and DFT calculations reveal that the Lewis acidic Zn-N sites promote step (2) by activating the alcohols. This is the first example of highly efficient single-atom catalysts for various organic transformations with biomass-derived alcohols as the alkylating reagents and hydrogen donors.
一种具有源自ZIF-8的普遍认为惰性的Zn-N基序的单原子催化剂，对于醇的活化出人意料地高效，能够实现醇介导的烷基化和转移氢化反应。腈、酮、醇、N-杂环、酰胺、酮酸和酯的C-烷基化，以及胺和酰胺的N-烷基化，采用所开发的方法均能顺利进行。以醇与腈的α-烷基化反应为例，α-烷基化反应首先是（1）氮掺杂碳载体催化醇脱氢生成醛，醛再与腈缩合生成乙烯基腈，接着是（2）乙烯基腈中的C=C键在Zn-N位点上进行转移氢化反应。实验结果和密度泛函理论计算表明，路易斯酸性的Zn-N位点通过活化醇来促进步骤（2）。这是以生物质衍生的醇作为烷基化试剂和氢供体用于各种有机转化的高效单原子催化剂的首个实例。
