Silica Nanoparticles Decorated with Polymeric Sulfonic Acids Trigger Selective Oxidation of Benzylic Methylenes to Aldehydic and Ketonic Carbonyls

Paris, Emanuele; Oldani, Claudio; Aricò, A.S.; D’Urso, Claudia; Bigi, Franca; Maestri, Giovanni; Pancrazzi, Francesco; Maggi, Raimondo

doi:10.1021/acssuschemeng.8b05845

Cited by 14 publications

(16 citation statements)

References 43 publications

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“…This correlates with analogous observations made during the study of related benzylic oxidations. [31] Upon depletion of its Bronsted acid sites, the material can be however reactivated by treatment with a sulfuric acid solution in order to restore its original loading of À SO 3 H groups. This approach allows to reuse the material for further experiments.…”

Section: Resultsmentioning

confidence: 99%

“…Taken together, these results strongly suggest that the dearomatization process occur through a radical mechanism, in analogy with related oxidations triggered by heterogeneous sulfonic acid previously developed by our group. [30][31][32] Finally, we attempted the oxidation of 1,4-naphthalene diol (7 a) under our optimized conditions. The starting material was completely consumed in 4 hours, affording 4 a in 90 % yield.…”

Section: Resultsmentioning

confidence: 99%

“…We then tried to tune the reactivity of perfluorinated polymers with sulfonic acid functions by supporting them onto silica. In particular, two materials in which Aquivion and Nafion decorate silica nanoparticles [31][32] were tested (entries 8-9). Although the overall yield of 2 a was disappointing in both cases (10 % and 22 %, respectively), the desired quinone formed selectively.…”

Section: Resultsmentioning

confidence: 99%

“…They can be used for instance to convert a variety of (aryl)methylene groups into the corresponding carbonyl derivatives (Scheme 1b). [31] This direct, double CÀ H functionalization is usually limited to a few transition-metal based complexes. An analogous approach enabled the development of a method for the synthesis of arylazo derivatives from the corresponding anilines (Scheme 1c).…”

Section: Introductionmentioning

confidence: 99%

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Oxidative Dearomatization of Phenols and Polycyclic Aromatics with Hydrogen Peroxide Triggered by Heterogeneous Sulfonic Acids

et al. 2021

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We report herein a method for the oxidative dearomatization of phenols and bare polycyclic arenes into the corresponding quinoid derivatives using hydrogen peroxide. The reaction is catalyzed by sulfonic acids and best results were achieved using heterogenized species. The best results using phenols were achieved using a hybrid material, namely a perfluorinated polymer functionalized with sulfonic acid groups supported on silica. The dearomatization of polycyclic aromatic hydrocarbons performed better using the polymeric acid catalyst. These methods operate under mild conditions, using mild and benign oxidants and thus minimizing the formation of waste.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Oxidative Dearomatization of Phenols and Polycyclic Aromatics with Hydrogen Peroxide Triggered by Heterogeneous Sulfonic Acids

et al. 2021

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“…Sulfonic acid FSs could catalyze the ester hydrolysis, dehydration of sorbitol, conversion of cellulose/glucose to levulinic acid, conversion of furfuryl alcohol to levulinic acid, selective oxidation of benzylic methylenes, glycerol acetalization and 5‐hydroxymethylfurfural etherification . Apart from sulfonic FSs, sulphonamide FS for alkylation and multicomponent coupling reactions, IL FS for the ketalization of cyclohexanone with glycol, amine FSs for Michael addition, and tertiary amine FS for the glucose isomerization have been reported.…”

Section: Applications and Advantages Of Fs‐based Catalystsmentioning

confidence: 99%

Functionalized Silicas for Metal‐Free and Metal‐Based Catalytic Applications: A Review in Perspective of Green Chemistry

Antony

Marimuthu

Yang

et al. 2019

The Chemical Record

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Heterogeneous catalysis plays a key role in promoting green chemistry through many routes. The functionalizable reactive silanols highlight silica as a beguiling support for the preparation of heterogeneous catalysts. Metal active sites anchored on functionalized silica (FS) usually demonstrate the better dispersion and stability due to their firm chemical interaction with FSs. Having certain functional groups in structure, FSs can act as the useful catalysts for few organic reactions even without the need of metal active sites which are termed as the covetous reusable organocatalysts. Magnetic FSs have laid the platform where the effortless recovery of catalysts is realized just using an external magnet, resulting in the simplified reaction procedure. Using FSs of multiple functional groups, we can envisage the shortened reaction pathway and, reduced chemical uses and chemical wastes. Unstable bio‐molecules like enzymes have been stabilized when they get chemically anchored on FSs. The resultant solid bio‐catalysts exhibited very good reusability in many catalytic reactions. Getting provoked from the green chemistry aspects and benefits of FS‐based catalysts, we confer the recent literature and progress focusing on the significance of FSs in heterogeneous catalysis. This review covers the preparative methods, types and catalytic applications of FSs. A special emphasis is given to the metal‐free FS catalysts, multiple FS‐based catalysts and magnetic FSs. Through this review, we presume that the contribution of FSs to green chemistry can be well understood. The future perspective of FSs and the improvements still required for implementing FS‐based catalysts in practical applications have been narrated at the end of this review.

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Ultrathin 2D Porphyrin‐Based Zr‐MOF Nanosheets as Heterogeneous Catalysts for Styrene Epoxidation and Benzylic C‐H Oxidation

Wang,

Ren,

Feng

et al. 2024

ChemCatChem

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Selective oxidation of hydrocarbons using molecular oxygen as sole oxidant under mild conditions remains a challenging task. In this context, metal‐organic frameworks (MOFs) have been widely used in various oxidation reactions due to their porosity, high surface area and designability. However, the slow diffusion of substrates/products in micropores of three‐dimensional (3D) bulk MOFs hinders the efficient catalytic performance of such materials. Herein an ultrathin two‐dimensional (2D) porphyrin‐based Zr‐MOF nanosheet (Zr‐TCPP) is synthesized through modulator‐control strategy. Subsequently, various metal ions are anchored into the porphyrin ring by post synthesis modification to afford a series of 2D Zr‐TCPP(M) (M=Mn, Fe, Co, Ni, Cu and Zn). Various structural characterization techniques indicate Zr‐TCPP(M) is nanoflower structure with ultrathin nanoplate petals which provides fully exposed accessible active sites. Among them, Zr‐TCPP(Fe) shows excellent catalytic performance in styrene epoxidation reactions and benzylic C‐H oxidation reactions using O2 as sole oxidant under ambient temperature and pressure. The remarkable activity arises from high density of exposed porphyrin‐Fe active sites, low diffusion barriers for substrates and products, as well as a similar homogeneous reaction space. Furthermore, Zr‐TCPP(Fe) nanosheet is easily recycled by centrifugation and reused at least five times without significant loss of catalytic activity.

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Silica Nanoparticles Decorated with Polymeric Sulfonic Acids Trigger Selective Oxidation of Benzylic Methylenes to Aldehydic and Ketonic Carbonyls

Cited by 14 publications

References 43 publications

Oxidative Dearomatization of Phenols and Polycyclic Aromatics with Hydrogen Peroxide Triggered by Heterogeneous Sulfonic Acids

Oxidative Dearomatization of Phenols and Polycyclic Aromatics with Hydrogen Peroxide Triggered by Heterogeneous Sulfonic Acids

Functionalized Silicas for Metal‐Free and Metal‐Based Catalytic Applications: A Review in Perspective of Green Chemistry

Ultrathin 2D Porphyrin‐Based Zr‐MOF Nanosheets as Heterogeneous Catalysts for Styrene Epoxidation and Benzylic C‐H Oxidation

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