Dataset Information

Identifying Radical Pathways for Cu(I)/Cu(II) Relay Catalyzed Oxygenation via Online Coupled EPR/UV-Vis/Near-IR Monitoring.

ABSTRACT: Copper-catalyzed C─H oxygenation has drawn considerable attention in mechanistic studies. However, a comprehensive investigation combining radical pathways with a metal-catalytic cycle is challenged by the intricate organic radicals and metallic intermediates. Herein, an online coupled EPR/UV-vis/near-IR detecting method is developed to simultaneously monitor both reactive radical species and copper complex intermediates during the reaction. Focusing on copper-catalyzed phenol oxygenation with cumene hydroperoxide, the short-lived alkylperoxyl radical (EPR signal at g = 2.0143) as well as the unexpected square planar Cu(II)-alkoxyl radical complex (near-IR signal at 833 nm) are unveiled during the reaction, in addition to the observable phenoxyl radical in EPR, quinone product in UV-vis, and Cu(II) center in EPR. With a comprehensive picture of diverse intermediates evolving over the same timeline, a novel Cu(I)/Cu(II) proposed relay-catalyzed sequential radical pathway. In this sequence, Cu(II) activates hydroperoxide through Cu(II)-OOR into the alkylperoxide radical, while the reaction between Cu(I) and hydroperoxide leads to Cu(II)(•OR)OH with high H-atom abstracting activity. These results provide a thorough understanding of the Cu(I)/Cu(II) relay catalysis for phenol oxygenation, setting the stage for mechanistic investigations into intricate radical reactions promoted by metallic complexes.

SUBMITTER: Wang Y

PROVIDER: S-EPMC11304242 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature

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Identifying Radical Pathways for Cu(I)/Cu(II) Relay Catalyzed Oxygenation via Online Coupled EPR/UV-Vis/Near-IR Monitoring.

Wang Yongtao Y Zhou Yujia Y Sun Wenjing W Wang Xinyu X Yao Jia J Li Haoran H

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20240529 29

Copper-catalyzed C─H oxygenation has drawn considerable attention in mechanistic studies. However, a comprehensive investigation combining radical pathways with a metal-catalytic cycle is challenged by the intricate organic radicals and metallic intermediates. Herein, an online coupled EPR/UV-vis/near-IR detecting method is developed to simultaneously monitor both reactive radical species and copper complex intermediates during the reaction. Focusing on copper-catalyzed phenol oxygenation with c ...[more]

PMID: 38810102

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Project description:One of the most important issues in the wine sector and prevention of adulterations of wines are discrimination of grape varieties, geographical origin of wine, and year of vintage. In this experimental research study, UV-Vis and FT-IR spectroscopic screening analytical approaches together with chemometric pattern recognition techniques were applied and compared in addressing two wine authentication problems: discrimination of (i) varietal and (ii) year of vintage of red wines produced in the same oenological region. UV-Vis and FT-IR spectra of red wines were registered for all the samples and the principal features related to chemical composition of the samples were identified. Furthermore, for the discrimination and classification of red wines a multivariate data analysis was developed. Spectral UV-Vis and FT-IR data were reduced to a small number of principal components (PCs) using principal component analysis (PCA) and then partial least squares discriminant analysis (PLS-DA) and linear discriminant analysis (LDA) were performed in order to develop qualitative classification and regression models. The first three PCs used to build the models explained 89% of the total variance in the case of UV-Vis data and 98% of the total variance for FR-IR data. PLS-DA results show that acceptable linear regression fits were observed for the varietal classification of wines based on FT-IR data. According to the obtained LDA classification rates, it can be affirmed that UV-Vis spectroscopy works better than FT-IR spectroscopy for the discrimination of red wines according to the grape variety, while classification of wines according to year of vintage was better for the LDA based FT-IR data model. A clear discrimination of aged wines (over six years) was observed. The proposed methodologies can be used as accessible tools for the wine identity assurance without the need for costly and laborious chemical analysis, which makes them more accessible to many laboratories.

Dataset Information

Identifying Radical Pathways for Cu(I)/Cu(II) Relay Catalyzed Oxygenation via Online Coupled EPR/UV-Vis/Near-IR Monitoring.

Publications

Identifying Radical Pathways for Cu(I)/Cu(II) Relay Catalyzed Oxygenation via Online Coupled EPR/UV-Vis/Near-IR Monitoring.

Similar Datasets

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