Theoretical studies and industrial applications of oxidative activation of inert C-H bond by metalloporphyrin-based biomimetic catalysis

Liu, Qiang; Guo, Can‐Cheng

doi:10.1007/s11426-012-4739-y

Cited by 26 publications

(16 citation statements)

References 117 publications

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“…120 A variety of oxygen donors ranging from molecular oxygen to peroxides, peracids, and iodosylbenzene are used for these reactions. 136 Due to ease, availability, cost and a greener approach, molecular oxygen in air is preferable as an oxygen donor because no energy is used to manufacture and store it.…”

Section: Substituted Fluorinated Porphyrinoids For Application In Matmentioning

confidence: 99%

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

et al. 2016

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Porphyrinoids are robust heterocyclic dyes studied extensively for their applications in medicine and as photonic materials because of their tunable photophysical properties, diverse means of modifying the periphery, and the ability to chelate most transition metals. Commercial applications include their use as phthalocyanine dyes in optical discs, porphyrins in photodynamic therapy, and as oxygen sensors. Most applications of these dyes require exocyclic moieties to improve solubility, target diseases, modulate photophysical properties, or direct the self-organization into architectures with desired photonic properties. The synthesis of the porphyrinoid depends on the desired application, but the de novo synthesis often involves several steps, is time consuming, and results in low isolated yields. Thus, the application of core porphyrinoid platforms that can be rapidly and efficiently modified to evaluate new molecular architectures allows researchers to focus on the design concepts rather than the synthesis methods, and opens porphyrinoid chemistry to a broader scientific community. We have focused on several widely available, commercially viable porphyrinoids as platforms: meso-perfluorophenylporphyrin, perfluoro-phthalocyanine, and meso-perfluorophenylcorrole. The perfluorophenylporphyrin is readily converted to the chlorin, bacteriochlorin, and isobacteriochlorin. Derivatives of all six of these core platforms can be efficiently and controllably made via mild nucleophilic aromatic substitution reactions using primary S, N, and O nucleophiles bearing a wide variety of functional groups. The remaining fluoro groups enhance the photo and oxidative stability of the dyes and can serve as spectroscopic signatures to characterize the compounds or in imaging applications using 19F NMR. This review provides an overview of the chemistry of fluorinated porphyrinoids that are being used as a platform to create libraries of photo-active compounds for applications in medicine and materials.

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Section: Substituted Fluorinated Porphyrinoids For Application In Matmentioning

confidence: 99%

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

et al. 2016

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“…23 These procedures are not the first choice from an environmental perspective because they require considerable amounts of stoichiometric additives and generate toxic waste products. 24 Therefore, developing effective methods for aerobic allylic oxidation of α-pinene with high selectivity is still highly desirable.…”

Section: Introductionmentioning

confidence: 99%

“…During the last decade, numerous research projects have shown that metalloporphyrins (MPs) are efficient and selective catalysts for aerobic oxidation of hydrocarbons to their oxyfunctionalized products in the absence of solvents and additives (co-catalysts, reductants, stoichiometric oxidants, and other additives). [24][25][26][27] Furthermore, compared with commercial catalysis in industrial processes, MP-based technology can be performed under mild conditions with significantly improved reaction conversions and product selectivities. The oxidation of simple hydrocarbons such as cyclohexane, cyclohexene, toluene, and other substrates has been widely studied.…”

Section: Introductionmentioning

confidence: 99%

Selective aerobic allylic oxidation of α-pinene catalyzed by metalloporphyrins in the absence of solvents and additives

Dong

Wang

et al. 2019

Journal of Chemical Research

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Selective aerobic oxidation of α-pinene to high-value products is a major challenge in chemistry. Metalloporphyrins are proved to be selective catalysts for aerobic oxidation of simple hydrocarbons. Herein, we extend this method to more complex substrates using metallodeuteroporphyrins as model catalysts. It was found that the oxidation occurs mainly on the C=C and allylic C–H bonds of α-pinene influenced by the reaction temperature, reaction time, catalyst concentration, and oxygen flow rate. Allylic C–H oxidation products are obtained with a maximum selectivity value of 78.4% using the following reaction conditions: 105°C, 7 h, 5 ppm, and 60 mL/min. The influence of the metal nuclei of the metallodeuteroporphyrins on this reaction is also investigated. It was found that metallodeuteroporphyrins with Fe3+ as the metal nucleus exhibit the highest catalytic activity.

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“…Metalloporphyrins are a class of highly efficient and selective Lewis acid catalyst and oxidative catalysts used for catalytic hydration (Tachinami et al 2013), C-C bond formation (Zhou et al 2012;Jiang et al 2013;Sheng et al 2013), and oxidation (Liu and Guo 2012). For instance, cobalt porphyrin has been used as a biomimetic catalyst for the industrial-scale oxidation of hydrocarbon with air under mild conditions (Liu and Guo 2012).…”

Section: Introductionmentioning

confidence: 99%

“…For instance, cobalt porphyrin has been used as a biomimetic catalyst for the industrial-scale oxidation of hydrocarbon with air under mild conditions (Liu and Guo 2012). It is worth noting that this biomimetic catalyst does not need to be recycled because of its very low concentration.…”

Section: Introductionmentioning

confidence: 99%

Biomimetic Conversion of Glucose to Organic Acid Facilitated by Metalloporphyrin under Mild Conditions

et al. 2016

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Biomimetic catalytic conversion of carbohydrates to low-molecular weight (LWM) organic acids was investigated in the presence of sulfonated metalloporphyrins (MTSPP, M = Fe, Mn, Co, Cu), with dioxygen as the oxidant. The results showed that the selectivity of lactic acid reached 70%, starting from glucose with an iron complex of meso-tetra(4-sulfonatophenyl)porphyrin (TSPPFeCl) as the catalyst at 433 K, and 0.6 MPa of O2 in 0.05 M NaOH aqueous solution. The effects of various metalloporphyrins on the selectivity of oxidative products were also considered. Experimental results show that TSPPFeCl exhibited the highest catalytic performance compared with TSPPMnCl, TSPPCo, and TSPPCu.

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Theoretical studies and industrial applications of oxidative activation of inert C-H bond by metalloporphyrin-based biomimetic catalysis

Cited by 26 publications

References 117 publications

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

Selective aerobic allylic oxidation of α-pinene catalyzed by metalloporphyrins in the absence of solvents and additives

Biomimetic Conversion of Glucose to Organic Acid Facilitated by Metalloporphyrin under Mild Conditions

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