Fe(NO3)3/NHPI-mediated co-oxidation of ketones and toluene for Baeyer-Villiger reaction with molecular oxygen

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL Applied Catalysis A: General Pub Date : 2025-02-25 Epub Date: 2025-01-01 DOI:10.1016/j.apcata.2024.120090

Haoran Yuan , Lingyao Wang , Siyi Li , Zejie Zhu , Jia Yao , Haoran Li , Yue Li , Junjie Qu

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Abstract

When oxygen is used as the oxidant in Baeyer-Villiger reaction, the excessive benzaldehyde is usually added as the sacrificial promoter, and the high price of benzaldehyde inhibits the development of this method. In this work, toluene, a much more feasible reagent comparing to benzaldehyde, was reported as a new drive for Baeyer-Villiger oxidation for the first time. Through the optimization of the metallic catalysts and solvents, the lactones are obtained accompanied with good yields of valuable benzaldehyde and benzoic acid under molecular oxygen atmosphere. Fe(NO₃)₃·9 H₂O and N-hydroxyphthalimide were used as the efficient catalysts which were compatible for the one-pot oxidation of toluene and cyclic ketones. The process analysis suggested that the benzoic peroxyacid generated from the oxidation of toluene is the dominant oxidant for the Baeyer-Villiger reaction of cyclic ketones. The intermediate analysis, ¹⁸O₂ labeling experiment and oxygen-free experiment revealed the critical role of O₂ and NO₃^- in the co-oxidation.

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Fe(NO3)3/ nhpi介导的酮和甲苯与分子氧的bayer - villiger反应共氧化

在Baeyer-Villiger反应中用氧作氧化剂时，通常加入过量的苯甲醛作为牺牲助剂，而苯甲醛的高昂价格阻碍了该方法的发展。本文首次报道了一种比苯甲醛更可行的甲苯作为Baeyer-Villiger氧化反应的新催化剂。通过对金属催化剂和溶剂的优化，在分子氧气氛下制得内酯，并有价苯甲醛和苯甲酸收率较高。采用Fe(NO3)3·9 H2O和n -羟基邻苯二胺作为一锅氧化甲苯和环酮的高效催化剂。工艺分析表明，甲苯氧化生成的苯甲酸是环酮Baeyer-Villiger反应的主要氧化剂。中间体分析、18O2标记实验和无氧实验揭示了O2和NO3-在共氧化过程中的关键作用。

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来源期刊

Applied Catalysis A: General 化学-环境科学

CiteScore

9.00

自引率

5.50%

发文量

415

审稿时长

24 days

期刊介绍： Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications. Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.