Bimetallic [Co/K] hydrogen evolution catalyst for electrochemical terminal C-H functionalization.

IF 15.7 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES

Nature Communications Pub Date : 2025-09-26 DOI:10.1038/s41467-025-63914-0

Sheng Zhang,Lei Hong,Jiayi Feng,Mohan Wang,Junyuan Hu,Ying Zhang,Man-Bo Li

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Abstract

Discovering novel catalysts for hydrogen evolution reaction (HER) holds the potential to revolutionize the energy chemistry and unlock new tool for synthetic processes. Inspired by hydrogenases, we pair alkali metals with cobalt-Salen catalysts which allow the integration of naked base site into bimetallic HER catalysts. The incorporation of alkali metals (Na, K, Rb, Cs) significantly enhances HER activity. Among these, the [Co/K] system exhibits the highest HER catalytic efficiency (kobs ~ 31.4 s⁻¹), which is 9 times higher than the mononuclear analogue. Remarkably, this HER catalyst is repurposed for the terminal C(sp³)-H functionalization of N-allylimines with imine/aldehyde, a previously inaccessible transformation. Mechanistic studies reveal that the naked base site enables selective C-H activation via proton relay, overriding the inherent preference for Pinacol coupling. The electrochemical protocol features good functional group tolerance, and opens up a streamlined avenue for chiral pyrrolines, key precursors of the anti-cancer medicine Larotrectinib. More importantly, the alkali metal effect is rationalized through structural analysis, density functional theory (DFT) calculations, and control experiments.

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电化学末端C-H功能化的双金属[Co/K]析氢催化剂

发现氢析反应（HER）的新型催化剂有可能彻底改变能源化学，并为合成过程解锁新的工具。受氢化酶的启发，我们将碱金属与钴- salen催化剂配对，从而将裸碱基整合为双金属HER催化剂。碱金属（Na， K, Rb, Cs）的掺入显著提高了HER活性。其中，[Co/K]体系表现出最高的HER催化效率（kbs ~ 31.4 s⁻），是单核类似物的9倍。值得注意的是，这种HER催化剂被重新用于n -烯基氨基与亚胺/醛的末端C（sp³）-H功能化，这是以前无法实现的转化。机制研究表明，裸碱基位点可以通过质子接力选择性地激活C-H，从而压倒对Pinacol偶联的固有偏好。电化学方案具有良好的官能团耐受性，并为手性吡咯啉开辟了一条流线型途径，吡咯啉是抗癌药物larorectinib的关键前体。更重要的是，通过结构分析、密度泛函理论（DFT）计算和控制实验来合理化碱金属效应。

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来源期刊

Nature Communications Biological Science Disciplines-

CiteScore

24.90

自引率

2.40%

发文量

6928

审稿时长

3.7 months

期刊介绍： Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.