Pd(II)/LA-catalyzed acetanilide olefination with dioxygen.

Transition-metal-catalyzed aromatic olefination through direct C-H activation represents an atom and step-economic route for versatile pharmaceutical syntheses, and in many cases, different stoichiometric oxidants are frequently employed for achieving a reasonable catalytic efficiency of the transition metal ions. Herein, we report a Lewis acid promoted Pd(II)-catalyzed acetanilide olefination reaction with atmospheric dioxygen as the oxidant source. The linkage of the Lewis acid to the Pd(II) species through a diacetate bridge significantly improved its catalytic efficiency, and independent kinetic studies on the olefination step revealed that adding the Lewis acid significantly accelerated the olefination rate as well as the C-H activation step. A strong basicity of the internal base in the Pd(II) salt also benefited the olefination reaction plausibly through base-assisted ß-hydride elimination.

Nickel(II)/Lewis acid catalysed olefin hydroamination and hydroarylation under mild conditions.

Aniline derivatives are important nitrogen-containing compounds with wide applications in chemicals, pharmaceuticals and agrochemicals. In the work described herein, nickel(II)/Lewis acid (LA) catalysed olefin hydroamination with anilines was explored for use in aniline derivative syntheses. The Ni(II)/LA catalysis proceeded smoothly under mild conditions, whereas using Ni(OAc)2 alone, the catalyst was inactive. Remarkably, the Markovnikov addition type products were obtained when substituted styrenes were used as the olefin source, while the anti-Markovnikov addition type products were obtained when the electron-deficient olefins such as acrylonitrile and acrylates were used. The mechanistic studies revealed that hydroamination of the styrene derivates proceeded via the amino-Ni(II)/LA attacking the carbocation intermediate which was generated by the protonation of the olefin, whereas for acrylonitrile and acrylates, it proceeded by a direct amino-Ni(II)/LA attack on the olefin by nucleophilic addition. In addition, the hydroarylation product was generated by the Hofmann-Martius rearrangement of the hydroamination product.

Physical conditioning methods for sludge deep dewatering: A critical review.

Sludge is an inevitable waste product of sewage treatment with a high water content and large volume, it poses a significant threat of secondary pollution to both water and the atmosphere without proper disposal. In this regard, dewatering has emerged as an attractive method in sludge treatment, as it can reduce the sludge volume, enhance its transportability and calorific value, and even decrease the production of landfill leachate. In recent years, physical conditioning methods including non-chemical conditioners or energy input alone, have been extensively researched for their potential to enhance sludge dewatering efficiency, such as thermal treatment, freeze-thaw, microwave, ultrasonic, skeleton builders addition, and electro-dewatering, as well as combined methods. The main objective of this paper is to comprehensively evaluate the dewatering capacity of various physical conditioning methods, and identify key factors affecting sludge dewatering efficiency. In addition, future research anticipated directions and outlooks are proposed. This work is expected to provide valuable insights for developing efficient, eco-friendly, and low-energy consumption techniques for deep sludge dewatering.

Unveiling the mechanisms of peracetic acid activation by iron-rich sludge biochar for sulfamethoxazole degradation with wide adaptability.

Advanced oxidation processes (AOPs) based on peracetic acid (PAA) has been extensively concerned for the degradation of organic pollutants. In this study, metallic iron-modified sludge biochar (Fe-SBC) was employed to activate PAA for the removal of sulfamethoxazole (SMX). The characterization results indicated that FeO and Fe2O3 were successfully loaded on the surface of the sludge biochar (SBC). Fe-SBC/PAA system achieved 92% SMX removal after 30 min. The pseudo-first-order kinetic reaction constant of the Fe-SBC/PAA system was 7.34 × 10-2 min-1, which was 2.4 times higher than the SBC/PAA system. The degradation of SMX was enhanced with increasing the Fe-SBC dosage and PAA concentration. Apart from Cl-, NO3- and SO42- had a negligible influence on the degradation of SMX. Quenching experiments and electron paramagnetic resonance (EPR) techniques identified the existence of reactive species, of which CH3C(O)OO•, 1O2, and O2•- were dominant reactive species in Fe-SBC/PAA system. The effect of different water matrices on the removal of SMX was investigated. The removal of SMX in tap water and lake water were 79% and 69%, respectively. Four possible pathways for the decay of SMX were presented according to the identification of oxidation products. In addition, following the ecological structure-activity relationship model (ECOSAR) procedure and the germination experiments with lettuce seeds to predict the toxicity of the intermediates. The acute and chronic ecotoxicity of SMX solution was dramatically diminished by processing with Fe-SBC/PAA system. In general, this study offered a prospective strategy for the degradation of organic pollutants.

Observing the Agostic Hydrogen in Pd(II)-Catalyzed Aromatic C-H Activation.

Direct C-H activation and functionalization offer a convenient protocol for pharmaceutical and material syntheses. Although versatile mechanisms have been proposed to depict transition-metal-catalyzed C-H activation, to date, the shared key agostic hydrogen intermediate in several major mechanisms has not been observed yet, which apparently puzzles the mechanism-based catalyst design. This work reports the direct observations of this intermediate in Pd(II)/Sc(III)-catalyzed C-H activation of acetanilides, and its stability and reactivity in C-H activation are investigated. Remarkably, this intermediate is only observed in electron-rich acetanilides, and the meta-substituent with increased σm constant generally accelerates C-H activation, a characteristic of the base-assisted C-H activation mechanism. This study has unveiled the masks of this intermediate with an understanding of its first-hand physicochemical properties, shedding new light on mechanism-based catalyst design.

Pd(II)/Lewis Acid Catalyzed Intramolecular Annulation of Indolecarboxamides with Dioxygen through Dual C-H Activation.

Transition-metal ion catalyzed intramolecular dual C-H activation to construct polycyclic heteroarene skeletons is merited for its step and atom-economic advantages in organic synthesis. However, in most cases, stoichiometric oxidants, elevated temperature, and other harsh conditions were commonly faced for this reaction, which apparently block the synthetic applications. Herein, we report a Pd(II)/LA (LA: Lewis acid) catalyzed intramolecular dual C-H activation to construct indoloquinolinone derivatives under mild conditions with dioxygen as the sole oxidant. It was found that adding LA such as Sc3+ to Pd(OAc)2 sharply improved its catalytic efficiency, whereas Pd(OAc)2 alone was very sluggish. The activity improvement was attributed to the linkage of the Sc3+ cation to the Pd(II) species through a diacetate bridge that significantly enhanced the electrophilic properties of Pd(II) for dual C-H activation.

Palladium(II)/Lewis Acid-Catalyzed Olefination of Arylacetamides with Dioxygen.

The present work introduces Pd(II)/LA-catalyzed (LA: Lewis acid) olefination of arylacetamides with dioxygen as the oxidant source. This protocol tolerates with different functional groups on the substrates, and the catalytic efficiency is highly Lewis acidity-dependent on added LA, that is, a stronger LA provided a better promotional effect. The 1H NMR studies of the semireaction between the arylacetamide and the Pd(II)/Sc(III) catalyst in HOAc-d4 disclosed the formation of a palladacycle intermediate, and the C-H activation step was reversible, which led to the formation of the deuterated arylacetamide substrate and the palladacycle intermediate. Further semireaction between the palladacycle intermediate and the olefin disclosed that it was a clean and much faster reaction than the C-H activation step, thus revealing multiple mechanistic information for Pd(II)-catalyzed C-H activation.

Pd(II)/Lewis acid catalyzed regioselective olefination of indole with dioxygen.

Transition metal ion catalyzed indole olefination through C-H activation is a convenient protocol to synthesize versatile bioactive vinylindole compounds; however, in most cases, stoichiometric amounts of oxidants were necessary to accomplish the catalytic cycle. The present study describes a Pd(II)/LA (LA: Lewis acid) catalyzed indole olefination with dioxygen as the sole oxidant. The olefination reaction with electron-rich olefins proceeded smoothly through the pyrrolyl N-carboxamide group directed remote C-H activation at the C3 position of the indole with the Pd(II)/LA catalyst, whereas Pd(II) alone was a very sluggish catalyst under identical conditions. For the electron-deficient olefins, the directing N-carboxamide group was not essential for olefination with this Pd(II)/LA catalyst, demonstrating a different olefination pathway from that of electron-rich olefins. Remarkably, 1H NMR kinetics disclosed that olefination proceeded much faster with electron-rich olefins than with electron-deficient ones.

Decarboxylative Addition of Propiolic Acids with Indoles to Synthesize Bis(indolyl)methane Derivatives with a Pd(II)/LA Catalyst.

Exploring new protocols for efficient organic synthesis is crucial for pharmaceutical developments. The present work introduces a Pd(II)/LA-catalyzed (LA: Lewis acid) decarboxylative addition reaction for the synthesis of bis(indolyl)methane derivatives. The presence of Lewis acid such as Sc(OTf)3 triggered Pd(II)-catalyzed decarboxylative addition of propiolic acids with indoles to offer the bis(indolyl)methane derivatives in moderate to good yields, whereas neither Pd(II) nor Lewis acid alone was active for this synthesis. The catalytic efficiency of Pd(OAc)2 was highly dependent on the Lewis acidity of the added Lewis acid, that is, a stronger Lewis acid provided a higher yield of the bis(indolyl)methane derivatives. Meanwhile, this Pd(II)/LA-catalyzed decarboxylative addition reaction showed good tolerance toward versatile electron-rich or -deficient substituents on the indole skeleton and on the benzyl ring of propiolic acids. The studies on the in situ 1H NMR kinetics of this Pd(II)/Sc(III) catalysis disclosed the formation of a transient vinyl-Pd(II)/Sc(III) intermediate generated by the pyrrole addition to the alkynyl-Pd(II)/Sc(III) species after decarboxylation, which was scarcely observed before.

Make it clean, make it safe: A review on virus elimination via adsorption.

Recently, the potential dangers of viral infection transmission through water and air have become the focus of worldwide attention, via the spread of COVID-19 pandemic. The occurrence of large-scale outbreaks of dangerous infections caused by unknown pathogens and the isolation of new pandemic strains require the development of improved methods of viruses' inactivation. Viruses are not stable self-sustaining living organisms and are rapidly inactivated on isolated surfaces. However, water resources and air can participate in the pathogens' diffusion, stabilization, and transmission. Viruses inactivation and elimination by adsorption are relevant since they can represent an effective and low-cost method to treat fluids, and hence limit the spread of pathogen agents. This review analyzed the interaction between viruses and carbon-based, oxide-based, porous materials and biological materials (e.g., sulfated polysaccharides and cyclodextrins). It will be shown that these adsorbents can play a relevant role in the viruses removal where water and air purification mostly occurring via electrostatic interactions. However, a clear systematic vision of the correlation between the surface potential and the adsorption capacity of the different filters is still lacking and should be provided to achieve a better comprehension of the global phenomenon. The rationalization of the adsorption capacity may be achieved through a proper physico-chemical characterization of new adsorbents, including molecular modeling and simulations, also considering the adsorption of virus-like particles on their surface. As a most timely perspective, the results on this review present potential solutions to investigate coronaviruses and specifically SARS-CoV-2, responsible of the COVID-19 pandemic, whose spread can be limited by the efficient disinfection and purification of closed-spaces air and urban waters.

Phosphate-lanthanum coated sewage sludge biochar improved the soil properties and growth of ryegrass in an alkaline soil.

The reclamation of alkaline soils remains challenging while the application of biochar has been proposed as a viable measure to rehabilitate soil fertility. The objective of the current pot study was to evaluate the efficacy of various P-La modified sewage sludge biochars (SSBC, La-SSBC, SSBC-P, La-SSBC-P) on soil phosphate-retention and ryegrass (Lolium perenne L.) growth in an alkaline soil (excess CaCO3). The results revealed that germination percentage, plant dry biomass, plant height, and the total amount of P in the ryegrass leaves were significantly (P < 0.05) improved under La-SSBC-P treatment as compared to other treatments. La-SSBC-P treatment significantly altered the chemical characteristics of post-harvest alkaline soil, such as pH, electrical conductivity (EC), cation exchange capacity (CEC), soil organic matter (SOM), limestone (CaCO3), phosphate, and lanthanum contents. In comparison to the SSBC treatment, soil available phosphorous (AP) contents under La-SSBC-P were enhanced by 6.7 times after loading biochar with P and La (La-SSBC-P). After the plantation of ryegrass, concentration of lanthanum in the soil was negligible. The contents of CaCO3 reduced by 76.2% after La-SSBC-P biochar treatment, compared to the cultivated control. This phenomenon clearly indicated that lanthanum was reduced due to the precipitation with limestone, which was proposed based on the data of X-ray diffraction (XRD) analysis. Overall, results showed that the P-loaded lanthanum decorated biochar (La-SSBC-P) could be used as a potential substitute for P-fertilizer under the experimental conditions. However, field experiments are required to confer the efficiency of La-SSBC-P as P fertilizer in different soils.

Emergency response to the explosive growth of health care wastes during COVID-19 pandemic in Wuhan, China.

During the Coronavirus Disease 2019 (COVID-19) as a worldwide pandemic, the security management of health care wastes (HCWs) has attracted increasing concern due to their high risk. In this paper, the integrated management of HCWs in Wuhan, the first COVID-19-outbreaking city with over ten millions of people completely locking down, was collected, investigated and analyzed. During the pandemic, municipal solid wastes (MSWs) from designated hospitals, Fangcang shelter hospitals, isolation locations and residential areas (e.g. face masks) were collected and categorized as HCWs due to the high infectiousness and strong survivability of COVID-19, and accordingly the average production of HCWs per 1000 persons in Wuhan explosively increased from 3.64 kg/d to 27.32 kg/d. Segregation, collection, storage, transportation and disposal of HCWs in Wuhan were discussed and outlined. Stationary facilities, mobile facilities, co-processing facilities (Incineration plants for MSWs) and nonlocal disposal were consecutively utilized to improve the disposal capacity, from 50 tons/d to 280.1 tons/d. Results indicated that stationary and co-processing facilities were preferential for HCWs disposal, while mobile facilities and nonlocal disposal acted as supplementary approaches. Overall, the improved system of HCWs management could meet the challenge of the explosive growth of HCWs production during COVID-19 pandemic in Wuhan. Furthermore, these practices could provide a reference for other densely populated metropolises.

Palladium(II)/Lewis Acid-Catalyzed Oxidative Olefination/Annulation of N-Methoxybenzamides: Identifying the Active Intermediates through NMR Characterizations.

Although Pd(II)-catalyzed C-H activation in arenes has been widely successful in organic synthesis with many palladacycle compounds isolated as the intermediates in ligand-directed C-H activation, direct identification of the reaction intermediates such as the π-complex prior to the C-H activation is still not successful because of their instability. In the present study, we introduce a Pd(II)/LA (LA: Lewis acid)-catalyzed oxidative olefination/annulation reaction between N-methoxybenzamides and acrylates with oxygen as the oxidant source, in which two intermediates, including an unsymmetrical η6-complex and a palladacycle species without the proton releasing to the environment, were identified through NMR characterizations. The in situ formation of the heterobimetallic Pd(II)/LA species such as Pd(II)/Sc(III) may have enhanced the electrophilic properties of the Pd2+ cation, thus improving the stability of the π-complex, herein, an unsymmetrical η6-complex, and improving its catalytic efficiency. The observed insensitive electronic effect preferred the concerted metalation-deprotonation (CMD) mechanism for this C-H activation, and the detected palladacycle intermediate without the proton releasing to the environment offered an experimental clue to support the proposed CMD mechanism.

Tuning of Persulfate Activation from a Free Radical to a Nonradical Pathway through the Incorporation of Non-Redox Magnesium Oxide.

Nonradical-based advanced oxidation processes for pollutant removal have attracted much attention due to their inherent advantages. Herein we report that magnesium oxides (MgO) in CuOMgO/Fe3O4 not only enhanced the catalytic properties but also switched the free radical peroxymonosulfate (PMS)-activated process into the 1O2 based nonradical process. CuOMgO/Fe3O4 catalyst exhibited consistent performance in a wide pH range from 5.0 to 10.0, and the degradation kinetics were not inhibited by the common free radical scavengers, anions, or natural organic matter. Quantitative structure-activity relationships (QSARs) revealed the relationship between the degradation rate constant of 14 substituted phenols and their conventional descriptor variables (i.e., Hammett constants σ, σ-, σ+), half-wave oxidation potential (E1/2), and pKa values. QSARs together with the kinetic isotopic effect (KIE) recognized the electron transfer as the dominant oxidation process. Characterizations and DFT calculation indicated that the incorporated MgO alters the copper sites to highly oxidized metal centers, offering a more suitable platform for PMS to generate metastable copper intermediates. These highly oxidized metals centers of copper played the key role in producing O2•- after accepting an electron from another PMS molecule, and finally 1O2 as sole reactive species was generated from the direct oxidation of O2•- through thermodynamically feasible reactions.

Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies.

Exploring new catalysts for efficient organic synthesis is among the most attractive topics in chemistry. Here, using Ni(OAc)2/LA as catalyst (LA: Lewis acid), a novel catalyst strategy was developed for oxidative coupling of thiols and phosphonates to phosphorothioates with oxygen oxidant. The present study discloses that when Ni(OAc)2 alone was employed as the catalyst, the reaction proceeded very sluggishly with low yield, whereas adding non-redox-active metal ions such as Y3+ to Ni(OAc)2 dramatically promoted its catalytic efficiency. The promotional effect is highly Lewis acidity dependent on the added Lewis acid, and generally, a stronger Lewis acid provided a better promotional effect. The stopped-flow kinetics confirmed that adding Y(OTf)3 can obviously accelerate the activation of thiols by Ni(II) and next accelerate its reaction with phosphonate to generate the phosphorothioate product. ESI-MS characterizations of the catalyst disclosed the formation of the heterobimetallic Ni(II)/Y(III) species in the catalyst solution. Additionally, this Ni(II)/LA catalyst can be applied in the synthesis of a series of phosphorothioate compounds including several commercial bioactive compounds. This catalyst strategy has clearly supported that Lewis acid can significantly improve the catalytic efficiency of these traditional metal ions in organic synthesis, thus opening up new opportunities in their catalyst design.

Facile synthesis of yolk shell Mn2O3@Mn5O8 as an effective catalyst for peroxymonosulfate activation.

Yolk shell Mn2O3@Mn5O8 was prepared through a facile synthetic procedure and was demonstrated to be a highly efficient and stable catalyst in peroxymonosulfate (PMS) activation for the catalytic degradation of organic contaminants. Mn2O3@Mn5O8 exhibits much improved activity compared with other classic manganese catalysts such as ε-MnO2, Mn2O3 and Mn3O4, and this performance was due to its yolk shell structure, mesoporous shell, well-defined interior voids, particular particle size and mixed valence states. The long-term stability and efficiency of Mn2O3@Mn5O8 was observed in activating PMS to generate sulfate radicals for the removal of various organic pollutants such as phenol, 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DP) and 2,4,6-trichlorophenol (2,4,6-TCP) in aqueous medium. The effects of the initial solution pH, influence of anions, catalyst stability and the temperature effect on 4-CP degradation were also investigated. Furthermore, electron paramagnetic resonance (EPR) spectroscopy and radical quenching tests were employed to investigate sulfate, hydroxyl, superoxide radicals and even 1O2 for organic degradation processes. Finally, a possible activation pathway of Mn2O3@Mn5O8/PMS was proposed that involved the inner-sphere interactions between the HSO5- and the catalyst surface, electron transfer from Mn species to PMS, and the generation of sulfate radicals. These findings provide new insights into PMS activation by using nano-particle catalysts of non-toxic metal oxides.

Nonredox Metal-Ions-Enhanced Dioxygen Activation by Oxidovanadium(IV) Complexes toward Hydrogen Atom Abstraction.

Dioxygen activation toward efficient catalysis at ambient temperature is still a big challenge for industrial oxidations, while it proceeds smoothly in nature. This work presents an example of that adding nonredox metal ions as Lewis acid can enhance dioxygen activation by oxidovanadium(IV) complex, [VIV(O)Cl(TPA)]PF6 (where TPA is tris-[(2-pyridy)methyl]amine), which leads to efficient hydrogen abstraction at ambient temperature, whereas, in the absence of a Lewis acid, the catalytic hydrogen abstraction of the oxidovanadium(IV) complex is very sluggish. Ultraviolet-visible light (UV-vis), electron paramagnetic resonance (EPR), mass, and nuclear magnetic resonance (NMR) studies have provided informative clues to indicate the interaction between the Lewis acid and vanadium complexes, including assisting the dissociation of the chloride from the oxidovanadium(IV) complex, interacting with the vanadium oxido group, and stabilizing the vanadium(V) superoxo species. These interactions enhanced the dioxgyen activation efficiency of oxidovanadium(IV) complex, and improved the hydrogen abstraction ability of vanadium(V) oxido species, which leads to efficient hydrogen abstraction in a catalytic process. A brief mechanism has also been proposed for dioxygen activation toward hydrogen abstraction by an oxidovanadium(IV) complex.

Nonredox Metal Ions Promoted Olefin Epoxidation by Iron(II) Complexes with H2O2: DFT Calculations Reveal Multiple Channels for Oxygen Transfer.

Nonredox metal ions play significant roles in a wide range of biological and chemical oxidations in which they can modulate the oxidative reactivity of those redox metal ions. With environmentally benign H2O2 as oxidant, the influence of nonredox metal ions on an iron(II) complex mediated olefin epoxidation was investigated through experimental studies and theoretical calculations. It was found that adding nonredox metal ions like Sc3+ can substantially improve the oxygen transfer efficiency of the iron(II) complex toward cyclooctene epoxidation even in the presence of certain amount of water. In 18O-labeling experiments with 18O water, the presence of Sc3+ provided a higher 18O incorporation in epoxide. In UV-vis studies, it was found that the presence of Sc3+ makes both FeIII-OOH and FeIV═O species unstable. Density functional theory calculations further disclosed that, in the presence of Sc(OTf)3, the Sc3+ adducts of FeIII-OOH and FeIV═O species are capable of epoxidizing olefin as well as FeV═O species, thus opening multiple channels for oxygenation. In particular, in the pathway of cyclooctene epoxidation, the FeIV═O/Sc3+ adduct-mediated epoxidation is more energetically favorable than that of the FeV═O species (12.2 vs 17.2 kcal/mol). This information may implicate that the presence of certain nonredox metal ions can facilitate these redox metal ions mediating biological and chemical oxidations happening at a relatively low oxidation state, which is more energetically accessible.

Non-redox metal ion promoted oxidative coupling of indoles with olefins by the palladium(ii) acetate catalyst through dioxygen activation: experimental results with DFT calculations.

Developing new catalytic technologies through C-H bond activation to synthesize versatile pharmaceuticals has attracted much attention in recent decades. This work introduces a new strategy in catalyst design for Pd(ii)-catalyzed C-H bond activation in which non-redox metal ions serving as Lewis acids play significant roles. In the oxidative coupling of indoles with olefins using dioxygen, it was found that Pd(OAc)2 alone as the catalyst is very sluggish at ambient temperature which provided a low yield of the olefination product, whereas adding non-redox metal ions to Pd(OAc)2 substantially improves its catalytic efficiency. In particular, it provided bis(indolyl)methane derivatives as the dominant product, a category of pharmacological molecules which could not be synthesized by Pd(ii)-catalyzed oxidative coupling previously. Detailed investigations revealed that the reaction proceeds by heterobimetallic Pd(ii)/Sc(iii)-catalyzed oxidative coupling of an indole with an olefin followed by Sc(iii)-catalyzed addition with a second indole molecule. DFT calculations disclosed that the formation of heterobimetallic Pd(ii)/Sc(iii) species substantially decreases the C-H bond activation energy barrier, and shifts the rate determining step from C-H bond activation of indole to the olefination step. This non-redox metal ion promoted Pd(ii)-catalyzed C-H bond activation may offer a new opportunity for catalyst design in organic synthesis, which has not been fully recognized yet.

The reactivity of the active metal oxo and hydroxo intermediates and their implications in oxidations.

While the significance of the redox metal oxo moieties has been fully acknowledged in versatile oxidation processes, active metal hydroxo moieties are gradually realized to play the key roles in certain biological oxidation events, and their reactivity has also been evidenced by related biomimic models. However, compared with the metal oxo moieties, the significance of the metal hydroxo moieties has not been fully recognized, and their relationships in oxidations remain elusive until recently. This review summarizes the reactivity of the metal oxo and hydroxo moieties in different oxidation processes including hydrogen atom transfer, oxygen atom transfer and electron transfer, and their reactivity similarities and differences have been discussed as well. Particularly, how the physicochemical properties like metal-oxygen bond order, net charge and potential of a redox metal ion affect its reactivity has also been presented based on available data. We hope that this review may provide new clues to understand the origins of the enzyme's choice on them in a specific event, to explain the elusive phenomena occurring in those enzymatic, homogeneous and heterogeneous oxidations, to design selective redox catalysts and control their reactivity.