Catalyst- and additive-free sunlight-induced autoxidation of aldehydes to carboxylic acids

Shi, Hongwei; Li, Jun; Wang, Tao; Rudolph, Matthias; Hashmi, A. Stephen K.

doi:10.1039/d2gc01429g

Cited by 21 publications

(33 citation statements)

References 67 publications

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“…Based on the above discussion and former literature, a possible mechanism for photoinduced B–V oxidation of cyclohexanone based on the Mukaiyama method through CR-SiW 12 is proposed in Scheme . Initially, CR-SiW 12 reaches its excited state [ CR-SiW 12 ]* under visible light (>400 nm) irradiation, then [ CR-SiW 12 ]* abstracts a hydrogen atom from benzaldehyde through the HAT process to generate C 6 H 5 CO • radical and H + [ CR-SiW 12 ] − . − The subsequent capture of O 2 by the C 6 H 5 CO • radical generates the C 6 H 5 COOO • radical. − Afterward, H + [ CR-SiW 12 ] − converts the C 6 H 5 COOO • radical to perbenzoic acid through the reverse HAT process and concurrently regenerates CR-SiW 12 back to the catalytic cycle . Finally, perbenzoic acid and cyclohexanone result in the formation of Criegee adduct intermediates, which undergo an intramolecular rearrangement to produce ε-caprolactone and benzoic acid. ,,, …”

Section: Resultsmentioning

confidence: 99%

Enhanced Photoinduced Baeyer–Villiger Oxidation of Ketones by Introducing Trinuclear Ruthenium Clusters into Polyoxometalate-Based Metal–Organic Frameworks

Liu

Wang

et al. 2023

Chem. Mater.

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The development of solar-driven organic synthesis processes as an alternative to conventional thermo-catalytic technologies is of great research significance in academia and industry. Herein, we looked into the photoinduced Baeyer−Villiger oxidation of cyclohexanone based on the Mukaiyama method for the first time. We fabricated a crystalline polyoxometalate-based metal−organic framework photocatalyst, CR-SiW 12 , which represents the first example of trinuclear ruthenium clusters involved in the construction of polyoxometalate-based metal−organic frameworks. The cyclohexanone was efficiently converted to ε-caprolactone under visible light (>400 nm) irradiation with CR-SiW 12 as the catalyst, with a reaction turnover number and turnover frequency recorded as 941 and 274.5 h −1 , respectively, and the apparent quantum yield at 465 nm was measured to be 8.4%. Moreover, CR-SiW 12 exhibited high structural stability and reaction reusability where reaction yield remained high at 91.3% after five consecutive reaction cycles. This work offers a promising strategy for accomplishing Baeyer−Villiger oxidation reactions under green conditions.

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Section: Resultsmentioning

confidence: 99%

Enhanced Photoinduced Baeyer–Villiger Oxidation of Ketones by Introducing Trinuclear Ruthenium Clusters into Polyoxometalate-Based Metal–Organic Frameworks

Liu

Wang

et al. 2023

Chem. Mater.

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“…Pentafluorobenzoic acid was synthesized by using pentafluorobenzoic acid, which was obtained by passing a stream of air through a solution of pentafluorobenzaldehyde in dry acetone for 8 h. The acid was isolated in quantitative yield as white crystals and used without further purification [ 42 ].…”

Section: Methodsmentioning

confidence: 99%

New Titanocene (IV) Dicarboxylates with Potential Cytotoxicity: Synthesis, Structure, Stability and Electrochemistry

Guk

Gibadullina

Burlutskiy

et al. 2023

IJMS

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The search for new anticancer drugs based on biogenic metals, which have weaker side effects compared to platinum-based drugs, remains an urgent task in medicinal chemistry. Titanocene dichloride, a coordination compound of fully biocompatible titanium, has failed in pre-clinical trials but continues to attract the attention of researchers as a structural framework for the development of new cytotoxic compounds. In this study, a series of titanocene (IV) carboxylate complexes, both new and those known from the literature, was synthesized, and their structures were confirmed by a complex of physicochemical methods and X-ray diffraction analysis (including one previously unknown structure based on perfluorinated benzoic acid). The comprehensive comparison of three approaches for the synthesis of titanocene derivatives known from the literature (the nucleophilic substitution of chloride anions of titanocene dichloride with sodium and silver salts of carboxylic acids as well as the reaction of dimethyltitanocene with carboxylic acids themselves) made it possible to optimize these methods to obtain higher yields of individual target compounds, generalize the advantages and disadvantages of these techniques, and determine the substrate frames of each method. The redox potentials of all obtained titanocene derivatives were determined by cyclic voltammetry. The relationship between the structure of ligands, the reduction potentials of titanocene (IV), and their relative stability in redox processes, as obtained in this work, can be used for the design and synthesis of new effective cytotoxic titanocene complexes. The study of the stability of the carboxylate-containing derivatives of titanocene obtained in the work in aqueous media showed that they were more resistant to hydrolysis than titanocene dichloride. Preliminary tests of the cytotoxicity of the synthesised titanocene dicarboxilates on MCF7 and MCF7-10A cell lines demonstrated an IC50 ≥ 100 μM for all the obtained compounds.

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“…Recently, several simple and eco-friendly methods for synthesizing aromatic acids by photoinduced oxidation of aldehydes were developed at room temperature [ 40 , 41 ]. However, there is no literature on preparation methods of aromatic acid from aromatic alcohols using O 2 as the sole oxidant under external catalyst-, additive-, and base-free conditions.…”

Section: Introductionmentioning

confidence: 99%

External Catalyst- and Additive-Free Photo-Oxidation of Aromatic Alcohols to Carboxylic Acids or Ketones Using Air/O2

Luo

et al. 2023

Molecules

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We present an environment-friendly and highly efficient method for the oxidation of aromatic alcohols to carboxylic acids or ketones in air via light irradiation under external catalyst-, additive-, and base-free conditions. The photoreaction system exhibits a wide substrate scope and the potential for large-scale applications. Most of the desired products are easily obtained via recrystallization and separation from low-boiling reaction medium acetone in good yields, and the products can be subsequent directly transformed without further purification.

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Catalyst- and additive-free sunlight-induced autoxidation of aldehydes to carboxylic acids

Abstract: A catalyst- and additive-free sunlight-induce strategy for autoxidation of a wide range of aldehydes to carboxylic acids is described for the first time. In this oxidation system, air as the...

Cited by 21 publications

References 67 publications

Enhanced Photoinduced Baeyer–Villiger Oxidation of Ketones by Introducing Trinuclear Ruthenium Clusters into Polyoxometalate-Based Metal–Organic Frameworks

Enhanced Photoinduced Baeyer–Villiger Oxidation of Ketones by Introducing Trinuclear Ruthenium Clusters into Polyoxometalate-Based Metal–Organic Frameworks

New Titanocene (IV) Dicarboxylates with Potential Cytotoxicity: Synthesis, Structure, Stability and Electrochemistry

External Catalyst- and Additive-Free Photo-Oxidation of Aromatic Alcohols to Carboxylic Acids or Ketones Using Air/O2

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