Solvent-scissors overcoming inert hydrogen bonding enable efficient oxidation of aromatic hydrocarbons under atmospheric oxygen

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis Pub Date : 2024-06-01 DOI:10.1016/S1872-2067(24)60042-2

Kui Jin , Meiyun Zhang , Penghua Che , Dongru Sun , Yong Wang , Hong Ma , Qiaohong Zhang , Chen Chen , Jie Xu

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引用次数: 0

Abstract

Hydrogen bonding is a fascinating interaction that controls the outcomes of chemical reactions. However, overcoming the strong deactivation arising from alterations in the polarity and electronic properties of the reactants and intermediates remains a challenge. Herein, we proposed a “solvent-scissors” strategy for overcoming the inert hydrogen bonding, enabling the efficient aerobic oxidation of methyl aromatics into aromatic acids under atmospheric oxygen at 25–45 °C. The hydrogen bonds between the key intermediate, benzaldehyde (PhCHO), and hexafluoroisopropanol (HFIP) were reconstructed using solvent-scissors (acetic acid (HOAc), ethyl acetate, ethyl chloroacetate, and methyl chloroacetate), which promoted the release of free PhCHO from its inert hydrogen-bonded state and enabled the one-step oxidation of toluene to benzoic acid under mild conditions. The standard Gibbs free energy changes (ΔG⁰) representing the proton acceptance capability of the solvent were of the same order of magnitude as the turnover number (TON) (capacity for promoting benzaldehyde oxidation). This approach affords remarkable benzoic acid selectivity (98.7%) with high toluene conversion (96.8%) at 45 °C within 4 h under 0.1 MPa O₂ using NHPI/metal acetate/HFIP-HOAc. This strategy opens up a new avenue for regulating hydrogen bonding in a wider range of applications for the planning and development of synthesis protocols.

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克服惰性氢键的溶剂剪刀能在大气氧条件下高效氧化芳香烃

氢键是一种控制化学反应结果的奇妙相互作用。然而，克服因反应物和中间产物的极性和电子特性改变而产生的强烈失活现象仍然是一项挑战。在此，我们提出了一种克服惰性氢键的 "溶剂-剪刀 "策略，使甲基芳烃在 25-45 °C 的大气氧条件下高效有氧氧化成芳香酸。利用溶剂剪刀（醋酸（HOAc）、醋酸乙酯、氯乙酸乙酯和氯乙酸甲酯）重建了关键中间体苯甲醛（PhCHO）和六氟异丙醇（HFIP）之间的氢键，促进了游离的 PhCHO 从惰性氢键状态中释放出来，使甲苯在温和条件下一步氧化成苯甲酸。代表溶剂质子接受能力的标准吉布斯自由能变化（ΔG0）与周转次数（TON）（促进苯甲醛氧化的能力）的数量级相同。使用 NHPI/醋酸乙烯酯/HFIP-HOAc，在 0.1 兆帕氧气条件下于 45 °C、4 小时内可获得显著的苯甲酸选择性（98.7%）和较高的甲苯转化率（96.8%）。这一策略为在更广泛的应用中调节氢键、规划和开发合成方案开辟了一条新途径。

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

Chinese Journal of Catalysis 工程技术-工程：化工

CiteScore

25.80

自引率

10.30%

发文量

235

审稿时长

1.2 months

期刊介绍： The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.