Modulation of ketyl radical reactivity to mediate the selective synthesis of coupling and carbonyl compounds

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)60045-8

Zhaohui Chen, Jun Deng, Yanmei Zheng, Wenjun Zhang, Lin Dong, Zupeng Chen

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Abstract

The importance of selective synthesis of high-value-added chemicals from renewable resources is paramount but remains a crucial challenge in organic synthesis and chemical reformation. Herein, we report the selective photosynthesis of C–C coupling products and carbonyl compounds from biomass-derived alcohols. The key to ensuring high end-to-end selectivity is the modulation of the reactivity of ketyl radical (*RCHOH) intermediates by employing different metal co-catalysts (Au, Pt, Pd, Ru) supported on Cd_0.6Zn_0.4S solid solution (CZS) photocatalysts. In particular, the C–C coupling product, hydrobenzion, and fully oxidized benzaldehyde were obtained from benzyl alcohol with high selectivity (> 98%) over Au-CZS and Ru-CZS, respectively. Combined experimental and theoretical analyses demonstrated that the affinity of *RCHOH for the surface of metals governs their subsequent transformations, in which weak and strong radical adsorption on Au and Ru results in C–C coupling products and carbonyl compounds, respectively.

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调节酮基的反应性以介导偶联物和羰基化合物的选择性合成

从可再生资源中选择性合成高附加值化学品至关重要，但这仍是有机合成和化学转化领域的一项关键挑战。在此，我们报告了从生物质衍生醇类中选择性光合合成 C-C 偶联产物和羰基化合物的过程。确保高端对端选择性的关键在于采用不同的金属助催化剂（金、铂、钯、钌），在 Cd0.6Zn0.4S 固溶体（CZS）光催化剂上支撑，调节酮基自由基（*RCHOH）中间体的反应活性。其中，在 Au-CZS 和 Ru-CZS 上分别以高选择性（> 98%）从苯甲醇中获得了 C-C 偶联产物氢苯并翁和完全氧化的苯甲醛。综合实验和理论分析表明，*RCHOH 对金属表面的亲和力决定了它们的后续转化，其中弱自由基和强自由基在 Au 和 Ru 上的吸附分别导致 C-C 偶联产物和羰基化合物的产生。

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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.