Bases Tuning Selective Aerobic Oxidation of Benzyl Alcohol to Benzaldehyde Catalyzed by Cu2+/TEMPO

IF 2.3 4区化学 Q3 CHEMISTRY, PHYSICAL Catalysis Letters Pub Date : 2024-11-13 DOI:10.1007/s10562-024-04843-3

Wenjie Yang, Fan Xu, Guojun Shi

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Abstract

Promotional role of basic ligands on the combination of cupric ions and 2,2,6,6-tetramethyl-piperidine-N-noxyl (Cu²⁺/TEMPO) was tried in the previous publications for selective aerobic oxidation of benzyl alcohol but a lack of a detailed investigation encourages us to perform further work. Here, Cu²⁺/TEMPO was used to catalyze selective aerobic oxidation of benzyl alcohol to benzaldehyde in the presence of bases, and triethylamine was found to be the best additive. A conversion of benzyl alcohol of 92.9% and a selectivity to benzaldehyde of 100% was observed in the presence of Cu²⁺/TEMPO/triethylamine. The promotion of triethylamine on Cu²⁺/TEMPO can be related to its capability in electron-donor and deprotonation. The speciation of the ternary catalyst combination was partially observed by the means of high-resolution mass spectroscopy (HRMS) and some key intermediates such as N-hydroxyl-2,2,6,6-tetramethylperidine (TEMPOH) and ethyl-substituted ammonium ions were confirmed. This study might provide some insights into the highly efficient transformation from benzyl alcohol to benzaldehyde and the promotion of bases on this transformation.

Graphical Abstract

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调谐 Cu2+/TEMPO 催化苯甲醇到苯甲醛的选择性有氧氧化的碱

在以前发表的关于选择性有氧氧化苯甲醇的文章中，尝试了碱性配体对铜离子和 2,2,6,6- 四甲基哌啶-N-羰基（Cu2+/TEMPO）组合的促进作用，但缺乏详细的研究促使我们开展进一步的工作。在此，我们使用 Cu2+/TEMPO 在碱存在下催化苯甲醇选择性有氧氧化为苯甲醛，并发现三乙胺是最佳添加剂。在 Cu2+/TEMPO/ 三乙胺存在下，苯甲醇的转化率为 92.9%，对苯甲醛的选择性为 100%。三乙胺对 Cu2+/TEMPO 的促进作用可能与其电子供体和去质子化能力有关。通过高分辨质谱法（HRMS）对三元催化剂组合的规格进行了部分观察，并确认了一些关键的中间产物，如 N-羟基-2,2,6,6-四甲基吡啶（TEMPOH）和乙基取代铵离子。这项研究可能会为苯甲醇到苯甲醛的高效转化以及碱对这种转化的促进作用提供一些启示。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Catalysis Letters 化学-物理化学

CiteScore

5.70

自引率

3.60%

发文量

327

审稿时长

1 months

期刊介绍： Catalysis Letters aim is the rapid publication of outstanding and high-impact original research articles in catalysis. The scope of the journal covers a broad range of topics in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis. The high-quality original research articles published in Catalysis Letters are subject to rigorous peer review. Accepted papers are published online first and subsequently in print issues. All contributions must include a graphical abstract. Manuscripts should be written in English and the responsibility lies with the authors to ensure that they are grammatically and linguistically correct. Authors for whom English is not the working language are encouraged to consider using a professional language-editing service before submitting their manuscripts.