Alkylene Oxide Research Articles

Copper‐Chitosan Beads as Efficient and Recyclable Heterogeneous Catalysts for C−H Oxidation and C−X Amination

AbstractUniform millimeter‐sized copper‐incorporated chitosan beads were easily prepared via a simple synthetic method as efficient bifunctional heterogeneous catalysts for C−H oxidation of alkylarenes to ketones and C−X amination of aryl halides with ammonia. These potent catalysts were compatible to various substrates, resulting in 2–97 and 39–99 % yields for the oxidation and amination reactions, respectively. Moreover, we highlight the dual roles of chitosan that it not only served as a versatile support to enhance the catalytic performance of copper active species, but it also acted as a base to promote the catalytic reactions. The catalysts are robust and could be employed under conventional heating or microwave irradiation for several times without deactivation or deformation. The bead shape of the catalysts provides easy separation and recyclability. Thus, chitosan and this preparation method may be exploited in the development of other transition metal catalyst beads for valuable organic reactions.

Highly thermally stable multi-porous calcium aluminum hydrotalcite catalyst for efficient carbonate synthesis

In the context of a carbon–neutral era, conversion of greenhouse gas CO2via chemical catalysis is a powerful means. Using CO2and petroleum-derived alkylene oxide as the raw materials to produce high-value carbonate substances has been considered a green and economic path for carbon reduction and energy transition. We discovered a multi-porous calcium aluminum hydrotalcite material (Ca-Al HT), and found that it performs excellent catalytic ability on transesterification (an important reaction in the synthesis of carbonates). Being different from homogeneous basic catalysts such as soluble metal hydroxides and organic halide salts, and well-known solid basic catalyst CaO, which are difficult to recycle and suffer severe deactivation in long-term catalytic process, the robust Ca12Al14O33crystal phase in Ca-Al HT catalyst behaves much more stable catalytic performance during 4000 min efficient catalysis (63 % conversion and 100 % selectivity). The special crystal phase structure of Ca12Al14O33remains stable at even a very high temperature of 900 °C. In contrast, CaO as the reference catalyst is very sensitive to trace H2O in catalytic system, and deactivates immediately. The outstanding catalytic ability of Ca-Al HT is attributed to its super-strong alkali strength, large alkali amount, and quick mass transfer originating from the hierarchical pore system.

Highly thermally stable multi-porous calcium aluminum hydrotalcite catalyst for efficient carbonate synthesis

<h2>Abstract</h2> In the context of a carbon-neutral era, conversion of greenhouse gas CO₂ via chemical catalysis is a powerful means. Using CO₂ and petroleum-derived alkylene oxide as the raw materials to produce high-value carbonate substances has been considered a green and economic path for carbon reduction and energy transition. We discovered a multi-porous calcium aluminum hydrotalcite material (Ca-Al HT), and found that it performs excellent catalytic ability on transesterification (an important reaction in the synthesis of carbonates). Being different from homogeneous basic catalysts such as soluble metal hydroxides and organic halide salts, and well-known solid basic catalyst CaO, which are difficult to recycle and suffer severe deactivation in long-term catalytic process, the robust Ca₁₂Al₁₄O₃₃ crystal phase in Ca-Al HT catalyst behaves much more stable catalytic performance during 4000 min efficient catalysis (63% conversion and 100% selectivity). The special crystal phase structure of Ca₁₂Al₁₄O₃₃ maintains stability at even a very high temperature of 900 °C. In contrast, CaO as the reference catalyst is very sensitive to trace H₂O in catalytic system, and deactivates immediately. The outstanding catalytic ability of Ca-Al HT is attributed to its super-strong alkali strength, large alkali amount, and quick mass transfer originating from the hierarchical pore system.

Palladium-Catalyzed Benzylic Oxidation of Alkylarenes with Water as an Oxygen Source

Key words palladium catalysis - oxidation - alkylarenes - water

Nanostructural Changes Correlated to Decay Resistance of Chemically Modified Wood Fibers

Reactive chemical modifications have been shown to impart decay resistance to wood. These modifications change hydroxyl availability, water uptake, surface energy, and the nanostructure of wood. Because fungal action occurs on the micro and nano scale, further investigation into the nanostructure may lead to better strategies to prevent fungal decay. The aim of this article is to introduce our findings using small angle neutron scattering (SANS) to probe the effects of chemical modifications on the nanostructure of wood fibers. Southern pine wood fiber samples were chemically modified to various weight percentage gains (WPG) using propylene oxide (PO), butylene oxide (BO), or acetic anhydride (AA). After modification, the samples were water leached for two weeks to remove any unreacted reagents, homopolymers or by-products and then the equilibrium moisture content (EMC) was determined. Laboratory soil-block-decay evaluations against the brown rot fungus Gloeophyllum trabeum were performed to determine weight loss and decay resistance of the modifications. To assist in understanding the mechanism behind fungal decay resistance, SANS was used to study samples that were fully immersed in deuterium oxide (D2O). These measurements revealed that modifying the fibers led to differences in the swollen wood nanostructure compared to unmodified wood fibers. Moreover, the modifications led to differences in the nanoscale features observed in samples that were exposed to brown rot fungal attack compared to unmodified wood fibers and solid wood blocks modified with alkylene oxides.

Selective Oxidation of Alkylarenes to the Aromatic Ketones or Benzaldehydes with Water.

Here a palladium-catalyzed oxidation method for converting alkylarenes into the aromatic ketones or benzaldehydes with water as the only oxygen donor is reported. This C-H bond oxidation functionalization does not require other oxidants and hydrogen acceptors, and H2 is the only byproduct. The oxygen atom introduced into the products is confirmed to be from water by the MS analysis on the product of the 18O-labeled water reaction.

Total Synthesis of the Proposed Structure of Tyloindane and Its Diastereoisomer

AbstractIt is intriguing that tyloindane, which was isolated together with phenanthroindolizidine alkaloids, contains no nitrogen atom. Attracted by its unique structure and uncovered biological activity, we synthesized the proposed structure of tyloindane and its diastereoisomer. To achieve this goal, several strategies that include an aryl/alkene oxidative coupling, radical cyclization, and intramolecular Parham alkylation, were explored. The 1H NMR data of the synthesized compounds do not match those of the isolated sample (tyloindane), indicating that the structure of tyloindane should be reassigned.

Two-Stage Catalysis in the Pd-Catalyzed Formation of 2,2,2-Trifluoroethyl-Substituted Acrylamides: Oxidative Alkylation of PdII by an IIII Reagent and Roles for Acetate, Triflate, and Triflic Acid

Two-Stage Catalysis in the Pd-Catalyzed Formation of 2,2,2-Trifluoroethyl-Substituted Acrylamides: Oxidative Alkylation of Pd^II by an I^III Reagent and Roles for Acetate, Triflate, and Triflic Acid

Small Angle Neutron Scattering Reveals Wood Nanostructural Features in Decay Resistant Chemically Modified Wood

While it is known that modifying the hydroxyls in wood can improve the decay resistance; what is often missing in the literature is whether these modifications alter wood nanostructure, and how these changes correlate to the improved decay resistance. Here, we used small angle neutron scattering (SANS) to probe the effects of alkylene oxide modifications on wood nanostructure. Southern pine wood samples were chemically modified to various weight percentage gains (WPG) using four different alkylene oxides: propylene oxide (PO), butylene oxide (BO), epichlorohydrin (EpH), and epoxybutene (EpB). After modification, the samples were water leached for 2 weeks to remove any unreacted reagents or homopolymers and then equilibrium moisture content (EMC) was determined at 90% relative humidity (RH) and 27°C. Laboratory soil block decay evaluations against the brown rot fungus Gloeophyllum trabeum were performed to determine weight loss and biological efficacy of the modifications. To assist in understanding the mechanism, SANS was used to study samples that were fully immersed in deuterium oxide (D2O). These measurements revealed that the modifications altered the water distribution inside the cell wall, and the most effective modifications reduced the microfibril swelling and preserved the microfibril structure even after being subject to 12 weeks of brown rot exposure.

On the limiting stage of oxidation of alkylarenes by potassium permanganate

The first stage of hydrocarbon benzyl C–H bond oxidation with permanganate is considered. Using a thermochemical approach, three possible mechanisms of this stage are analyzed: electron transfer from hydrocarbon to oxidant, homolytic abstraction of H-atom from benzyl C–H bond, insertion of O-atom into benzyl C–H bond. The reaction enthalpies were used as a characteristic of the thermodynamic favorability of these reactions. The thermochemical characteristics of the species involved in oxidation reactions and the reaction enthalpies were calculated with the quantum chemical method PM7. It is the most accurate among the semi-empirical methods. The calculated reaction enthalpies of various oxidant species formed during the oxidation of the cumene with KMnO 4 showed that their reactivity increases in the series MnO 4 – &lt; HMnO 4 &lt; H 2 MnO 4 + &lt; MnO 3 + . It is established that the protonation of the oxidant species increases their reactivity both in homolytic reactions, where after the neutral H-atom abstraction free radical is formed, and in heterolytic ones, when electron or hydride ion transfer occurs. The obtained fact of increasing the reactivity of the species in oxidation reactions due to protonation explains the experimentally established significant effect of medium acidity on the rate of permanganate reactions with C–H bonds in hydrocarbon functionalization processes, and also provides understanding of the significant role of acidity in the oxidation of organic matter by permanganate. It should be noted that dehydration (removal of water molecule) of the oxidant species increases its reactivity in oxidation reactions. The results of the calculations of the enthalpies of the reactions show greater thermochemical favorability of hydride ion transfer reactions in comparison with reactions that proceed through homolysis of the C–H bond is shown. Keywords: potassium permanganate, oxidative functionalization, alkylarenes, PM7 method.

Visible-light-promoted radical cascade alkylation/cyclization: access to alkylated indolo/benzoimidazo[2,1-a]isoquinolin-6(5H)-ones.

A new protocol is herein described for the direct generation of alkylated indolo/benzoimidazo[2,1-a]isoquinolin-6(5H)-one derivatives by using Hantzsch esters as alkylation radical precursors using a photoredox/K2S2O8 system. This oxidative alkylation of active alkenes involves a radical cascade cyclization process and a sequence of Hantzsch ester single electron oxidation, C-C bond cleavage, alkylation, arylation and oxidative deprotonation.

HCl-Catalyzed Aerobic Oxidation of Alkylarenes to Carbonyls.

The construction of C-O bonds through C-H bond functionalization remains fundamentally challenging. Here, a practical chlorine radical-mediated aerobic oxidation of alkylarenes to carbonyls was developed. This protocol employed commercially available HCl as a hydrogen atom transfer (HAT) reagent and air as a sustainable oxidant. In addition, this process exhibited excellent functional group tolerance and a broad substrate scope without the requirement for external metal and oxidants. The mechanistic hypothesis was supported by radical trapping, 18 O labeling, and control experiments.

Fe(II)-phthalocyanine supported on chitosan aerogel as a catalyst for oxidation of alcohols and alkyl arenes

Manipulation of materials is considered as one of the eminent strategies to create desirable catalysts. In this regard, increasing surface area and decreasing dimensions of catalysts have been widely employed on account of effectiveness of these methods. Herein, aerogel form of chitosan as a sustainable, and high aspect ratio compound is employed as a green support for the catalytic purposes. Chitosan aerogel was modified with Fe(II)-phthalocyanine to produce a heterogeneous catalyst for oxidation reactions. The synthesized catalyst promoted the oxidation reactions of alcohols and alkyl arenes to the corresponding aldehydes and ketones using H2O2 as an oxidant in 24 h. The reactions for aliphatic and aromatic alcohols gave turnover numbers of 106–109 at 80 °C and 106–117 at room temperature, respectively. The oxidations of alkyl arenes were carried out with turnover numbers laying in the range of 106–117 at 100 °C. The low toxicity, inexpensive nature, and recycling possibility of the catalyst accompanied by the reaction mild conditions, clean oxidant, and excellent yields offer chitosan aerogel modified with Fe(II)-phthalocyanine as a promising catalyst for oxidation reactions.

Efficacy and safety of a novel hemostatic material, BoneStat, compared with Ostene and Bone Wax in a rat calvarial defect model.

Hemostasis has critical significance during surgical procedures. Bone Wax has traditionally been commonly used for bone hemostasis despite well-documented undesirable side effects: hindering osteogenesis and induction of inflammatory reactions with consequent increase in infection rates. A later developed formulation, Ostene, offers an alternative to Bone Wax with lesser undesired effects. In this study, BoneStat, a newly developed bone hemostatic formulation comprising water-soluble alkylene oxide co-polymers, was evaluated for water solubility, hemostatic efficacy, ease of handling, bone healing efficacy, and inflammatory reactions compared with Bone Wax and Ostene in a rat calvarial defect model. More than 95% of BoneStat was dissolved in water within 48 h, as was Ostene, but not Bone Wax. The time to hemostasis using BoneStat was significantly faster than with Ostene or Bone Wax. BoneStat also improved ease of handling compared to Ostene or BoneWax. BoneStat- and Ostene-treated groups constantly showed better bone healing than with Bone Wax. The BoneStat and Ostene groups presented no evidence of chronic inflammation reaction contrary to Bone Wax. These results suggest improved hemostasis, ease of handling, non-hindering bone healing, and unnoticeable chronic inflammatory reactions with BoneStat. Thus, Bonestat is a useful and reliable formulation for mechanical hemostasis.

Cyclic and Acyclic Amine Oxide Alkyl Derivatives as Potential Adjuvants in Antimicrobial Chemotherapy against Methicillin-Resistant Staphylococcus aureus with an MDR Profile

The dramatic intensification of antimicrobial resistance occurrence in pathogenic bacteria concerns the global community. The revitalisation of inactive antibiotics is, at present, the only way to go through this health system crisis and the use of antimicrobial adjuvants is turning out the most promising approach. Due to their low toxicity, eco-friendly characteristics and antimicrobial activity, amphoteric surfactants are good candidates. This study investigated the adjuvant potentialities of commercial acyclic and newly cyclic N-oxide surfactants combined with therapeutically available antibiotics against MDR methicillin-resistant Staphylococcus aureus (MRSA). The safety profile of the new cyclic compounds, compared to commercial surfactants, was preliminarily assessed, evaluating the cytotoxicity on human peripheral mononuclear blood cells and the haemolysis in human red blood cells. The compounds show an efficacious antimicrobial activity strongly related to the length of the carbon atom chain. In drug–drug interaction assays, all surfactants act synergistically, restoring sensitivity to oxacillin in MRSA, with dodecyl acyclic and cyclic derivatives being the most effective. After evaluating the cytotoxicity and considering the antimicrobial action, the most promising compound is the L-prolinol amine-oxide C12NOX. These findings suggest that the combination of antibiotics with amphoteric surfactants is a valuable therapeutic option for topical infections sustained by multidrug-resistant S. aureus.

Mixed hetero-/homogeneous TiO2/N-hydroxyimide photocatalysis in visible-light-induced controllable benzylic oxidation by molecular oxygen

Homogeneous and heterogeneous types of catalysis are frequently considered as separate disciplines or even opposed to each other. In the present work, a new type of mixed hetero-/homogeneous catalysis was demonstrated for the case of selective alkylarene oxidation by molecular oxygen. The proposed catalytic system consists of two widely available components: N-hydroxyphthalimide (NHPI, a homogeneous organocatalyst for free-radical chain reactions) and nanosized TiO2 (heterogeneous UV-active photoredox catalyst). The interaction of NHPI with TiO2 allows for a shift from UV to visible light photoredox activity and generation of phthalimide-N-oxyl (PINO) radicals that diffuse into the solution where NHPI/PINO-catalyzed free-radical chain reaction can proceed without the additional light input providing a fundamental increase in energy efficiency. The NHPI/TiO2 ratio controls the selectivity of oxidation affording preferential formation of hydroperoxide or ketone from alkylarene.

Synthesis of functional and architectural polyethers via the anionic ring-opening polymerization of epoxide monomers using a phosphazene base catalyst

This focused review provides an overview of our recent work and related research regarding the precise anionic ring-opening polymerization (AROP) of substituted epoxides, including alkylene oxides, glycidyl ethers, and glycidyl amines, using t-Bu-P4 as the phosphazene base catalyst to produce functional polyethers, such as homopolymers, block copolymers (BCPs), and topologically unique polymers. First, the fundamental aspects and applicable monomer scope of t-Bu-P4-catalyzed AROP are discussed. Subsequently, the applications of well-defined polyethers prepared via t-Bu-P4-catalyzed AROP to develop functional materials, such as thermoresponsive polymers and Li+ conducting polymers, are discussed. Finally, the utility of t-Bu-P4-catalyzed AROP in the precise synthesis of star-shaped, cyclic, and multicyclic polymers is presented. Overall, we intend to illustrate the exploitable utility of the present polymerization system for fundamental and advanced polymer research. This focused review provides an overview of our recent work and related research regarding the precise anionic ring-opening polymerization (AROP) of substituted epoxides, including alkylene oxides, glycidyl ethers, and glycidyl amines, using t-Bu-P4 as the phosphazene base catalyst to produce functional polyethers, such as homopolymers, block copolymers (BCPs), and topologically unique polymers. First, the fundamental aspects and applicable monomer scope of the t-Bu-P4-catalyzed AROP are discussed. Subsequently, the applications of the AROP system for synthesizing functional materials and architectural polymers are presented.

Precious Metal-Free LaMnO3 Perovskite Catalyst with an Optimized Nanostructure for Aerobic C-H Bond Activation Reactions: Alkylarene Oxidation and Naphthol Dimerization.

In this article, we describe the development of a new aerobic C-H oxidation methodology catalyzed by a precious metal-free LaMnO3 perovskite catalyst. Molecular oxygen is used as the sole oxidant in this approach, obviating the need for other expensive and/or environmentally hazardous stoichiometric oxidants. The electronic and structural properties of the LaMnO3 catalysts were systematically optimized, and a reductive pretreatment protocol was proved to be essential for acquiring the observed high catalytic activities. It is demonstrated that this newly developed method was extremely effective for the oxidation of alkylarenes to ketones as well as for the oxidative dimerization of 2-naphthol to 1,1-binaphthyl-2,2-diol (BINOL), a particularly important scaffold for asymmetric catalysis. Detailed spectroscopic and mechanistic studies provided valuable insights into the structural aspects of the active catalyst and the reaction mechanism.

Nickel-catalyzed site- and stereoselective reductive alkylalkynylation of alkynes

Nickel-catalyzed site- and stereoselective reductive alkylalkynylation of alkynes

Correction: Rhodium(iii)-catalyzed oxidative alkylation of N-aryl-7-azaindoles with cyclopropanols.

Correction for 'Rhodium(iii)-catalyzed oxidative alkylation of N-aryl-7-azaindoles with cyclopropanols' by Jidan Liu et al., Org. Biomol. Chem., 2021, DOI: .