Rearrangement Reactions Research Articles

Synthesis of Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3-Indolylmethanols.

Catalytic enantioselective preparation of alkene atropisomers with multiple stereogenic elements and discovery of their applications have become significant but challenging issues in the scientific community due to the unique structures of this class of atropisomers. We herein report the first catalytic atroposelective preparation of cyclopentenyl[b]indoles, a new kind of alkene atropisomers, with stereogenic point and axial chirality via an unusual rearrangement reaction of 3-indolylmethanols under asymmetric organocatalysis. Notably, this novel type of alkene atropisomers have promising applications in developing chiral ligands or organocatalysts, discovering antitumor drug candidates and fluorescence imaging materials. Moreover, the theoretical calculations have elucidated the possible reaction mechanism and the non-covalent interactions to control the enantioselectivity. This approach offers a new synthetic strategy for alkene atropisomers with multiple stereogenic elements, and represents the first catalytic enantioselective rearrangement reaction of 3-indolylmethanols, which will advance the chemistry of atropisomers and chiral indole chemistry.

Manifesting the multi-stimuli-responsive behaviour of triazole-substituted triphenylamine.

The development of multi-stimuli-responsive (MSR) materials is a tempting yet intriguing challenge due to the absence of a defined design approach. In this study, we designed and synthesised two compounds based on triphenylamine, namely, TPA-Tz1 and TPA-Tz2. The photoluminescent investigations reveal the MSR behaviour of both compounds. TPA-Tz1 shows reversible mechanochromism with a blue-shifted emission due to changes in intermolecular interactions. Furthermore, both compounds exhibit solvatochromism in solvents of varying polarity. Detailed studies suggest that solvatochromism in TPA-Tz1 can be attributed to twisted intramolecular charge transfer (TICT), while in TPA-Tz2, it is due to intramolecular charge transfer (ICT). Additionally, both compounds display acidochromic properties in solution as well as in the solid state due to the protonation of the triazole ring. All changes in emissions are corroborated through theoretical calculations. The results provide insights into the intricate interplay of molecular interactions and structural rearrangements that contribute to the compound's multifaceted responsiveness.

A low-temperature co-treatment of diethylhexyl phthalate-rich polyvinyl chloride and waste copper catalyst by subcritical water (hydrothermal treatment): Dechlorination, recovery of diethylhexyl phthalate and copper

As one of the most widespread plastics in the world, the recycling of diethylhexyl phthalate-rich polyvinyl chloride (DEHP-rich PVC) faces great challenges because of the high levels of Cl and plasticizers. On the other hand, waste copper catalyst (WCC) discharged from various industrial processes is not effectively recycled. In this study, a significant synergistic effect between the DEHP-rich PVC and WCC was found in a subcritical water (SubCW) medium, and a co-treatment of the DEHP-rich PVC and WCC was developed by the SubCW process. The introduction of WCC significantly improved the dechlorination efficiency of the DEHP-rich PVC to 96.03 % at a low temperature of 250 °C. Under the optimal conditions, the leaching of copper from WCC reached a maximum of 81.08 %. Oil products included DEHP (55.7 %, GC peak area%), 3-methyl-3-heptene (37.3 %, GC peak area%), and 2-ethyl-1-hexanol (7.0 %, GC peak area%). The dechlorination pathways of the DEHP-rich PVC included hydroxyl substitution and direct dechlorination. HCl released from the DEHP-rich PVC led to a decrease in the pH of the system and significant copper leaching from the WCC. DEHP was decomposed by hydrolysis, dehydration, and rearrangement reaction by the SubCW co-treatment process. The enhancement mechanism of the WCC for the dechlorination of the DEHP-rich PVC was based on that the conversion of copper species in the SubCW promoted the formation of hydroxyl radicals and the hydroxyl substitution for chlorine in PVC molecular chain. The proposed SubCW low-temperature co-treatment could be a prospective strategy for the low-energy and synchronous recovery of the two different wastes of the DEHP-rich PVC and WCC.

Palladium-Catalyzed Synthesis of β-Alkynyl Ketones via Selective 1,3-Alkynyl Migration of α,α-Disubstituted Allylic Alcohols.

Herein, a palladium-catalyzed 1,3-alkynyl migration of allylic alcohol for the synthesis of β-alkynyl ketone was described. This intramolecular rearrangement reaction demonstrated an enhanced reactivity compared to the traditional intermolecular alkynylation by circumventing the dimerization of alkynes, exhibiting a specific selectivity toward β-alkynyl elimination. Moreover, this reaction featured wide substrate scope, good functional group tolerance, and 100% atom economy.

Silica-Ti3C2Tx MXene Nanoarchitectures with Simultaneous Adsorption and Photothermal Properties.

Layered Ti3C2Tx MXene has been successfully intercalated and exfoliated with the simultaneous generation of a 3D silica network by treating its cationic surfactant intercalation compound (MXene-CTAB) with an alkoxysilane (TMOS), resulting in a MXene-silica nanoarchitecture, which has high porosity and specific surface area, together with the intrinsic properties of MXene (e.g., photothermal response). The ability of these innovative MXene silica materials to induce thermal activation reactions of previously adsorbed compounds is demonstrated here using NIR laser irradiation. For this purpose, the pinacol rearrangement reaction has been selected as a first model example, testing the effectiveness of NIR laser-assisted photothermal irradiation in these processes. This work shows that Ti3C2Tx-based nanoarchitectures open new avenues for applications that rely on the combined properties inherent to their integrated nanocomponents, which could be extended to the broader MXene family.

Switchable Synthesis of Tritylone Alcohols and 2-Benzoylbenzoate Esters from Spiroindane-1,3-diones.

A solvent-controlled regioselective rearrangement reaction of spiroindane-1,3-diones with a leaving group has been developed. In acetonitrile solvent, the spiroindane-1,3-diones 3 were rearranged to provide tritylone alcohols, while 2-benzoylbenzoate ester derivatives were obtained if the reactions were performed in alcohols.

Spectroscopic Characterization of the 1-Boratricyclo-[4.1.0.02,7]-heptane Radical with a Delocalized Four-Center-One-Electron Bond.

The boron atom is a highly electrophilic reagent due to the presence of its empty p orbital, making it prone to undergo electrophilic addition reactions with the carbon-carbon double bonds of olefins. In this study, the classical C=C reaction pathway occurs when a boron atom attacks the C=C bond of cyclohexene, resulting in the formation of the η2 (1,2)-BC6H10 complex (A) that contains a borirane radical subunit. This complex can further undergo photoisomerization, leading to the formation of a 3,4,5,6-tetrahydroborepine radical (C) through the cleavage of C-C bonds. In addition, two 1-boratricyclo[4.1.0.02,7]heptane radicals with chair (B) and boat (B') conformations were observed through α C-H cleavage reactions. Bonding analysis indicates that these radicals involve a four-center-one-electron (4c-1e) bond. Under UV light irradiation, these two radicals undergo ring-opening and rearrangement reactions, resulting in the formation of a 1-cyclohexen-1-yl-borane radical (D), which is a sp2 C-H activation product. These findings delineate a potential pathway for the synthesis of organoboron radicals through boron-mediated C-H and C-C bond cleavage reactions in cycloolefins.

(Invited) Thermally Selective Skeletal Rearrangements at Interfaces

Thermal rearrangements, in which an atom, ion or chemical unit of a molecule is rearranged to obtain a structural isomer of the original molecule under a thermal stimulus, represents an excellent alternative to induce the formation of novel antiaromatic PCHs and conjugated polymers not accessible otherwise. Only recently, a few strain-induced rearrangement reactions of precursors that are composed of rigid and strained three dimensional (3D) structures have shown skeletal rearrangements in their backbone after planarization on metal surfaces. In this respect, the selectivity of on-surface chemical reaction pathways is a promising approach to increase synthetic versatility, though remains largely underexplored. In this talk I will review our recent discoveries regarding the exploitation of thermal rearrangements to form 0D, 1D and 2D unique molecular nanocarbons.

Integrative experimental and computational analysis of the impact of KGM's polymerization degree on wheat starch's pasting and retrogradation characteristics

This study investigated the influence of Konjac Glucomannan (KGM) with varying degrees of polymerization (DKGMx) on the gelatinization and retrogradation characteristics of wheat starch, providing new insights into starch-polysaccharide interactions. This research uniquely focuses on the effects of DKGMx, utilizing multidisciplinary approaches including Rapid Visco Analysis (RVA), Differential Scanning Calorimetry (DSC), rheological testing, Low-Field Nuclear Magnetic Resonance (LF-NMR), and molecular simulations to assess the effects of DKGMx on gelatinization temperature, viscosity, structural changes post-retrogradation, and molecular interactions. Our findings revealed that higher degrees of polymerization (DP) of DKGMx significantly enhanced starch's pasting viscosity and stability, whereas lower DP reduced viscosity and interfered with retrogradation. High DP DKGMx promoted retrogradation by modifying moisture distribution. Molecular simulations revealed the interplay between low DP DKGMx and starch molecules. These interactions, characterized by increased hydrogen bonds and tighter binding to more starch chains, inhibited starch molecular rearrangement. Specifically, low DP DKGMx established a dense hydrogen bond network with starch, significantly restricting molecular mobility and rearrangement. This study provides new insights into the role of the DP of DKGMx in modulating wheat starch's properties, offering valuable implications for the functional improvement of starch-based foods and advancing starch science.

Synthesis of 2‐Aminopyridine Derivatives via a Tandem CuAAC/Ring‐Cleavage/[4+2]‐Cycloaddition/Rearrangement Reaction Sequence

Abstract2H‐Azirines are an important class of small‐ring heterocycle that have been employed as versatile synthetic building blocks. Herein, a one‐pot CuAAC/ring‐cleavage/[4+2]‐cycloaddition/rearrangement reaction sequence involving terminal ynones, sulfonyl azides and 2H‐azirines is reported that leads to 2‐aminopyridine derivatives. In the first step, highly reactive N‐sulfonyl α‐acylketenimines are generated, via a CuAAC/ring‐cleavage process, from sulfonyl azides and terminal ynones and these undergo inverse electron‐demand Diels–Alder cycloaddition reactions with 2H‐azirines to form (isolable) 1,3‐oxazines that themselves undergo base‐promoted ring‐cleavage and rearrangement reactions to afford the title compounds.

A Highly Sustainable Supramolecular Bioplastic Film with Superior Hydroplasticity and Biodegradability.

Massive accumulation of postconsumer plastic waste in eco-system has raised growing environmental concerns. Sustainable end-of-life managements of the indispensable plastic are highly demanding and challenging in modern society. To relieve the plastic menace, herein we present a full life cycle sustainable supramolecular bioplastic made from biomass-derived polyelectrolyte (chitosan quaternary ammonium salt, QCS) and natural sodium fatty acid (sodium laurate, SL) through solid-phase molecular self-assembly (SPMSA), by which the QCS-SL complexes, precipitated from mixing the aqueous solutions, self-assemble to form bioplastic film by mildly pressing at room temperature. The QCS-SL bioplastic films display superior hydroplasticity owing to the water-activated molecular rearrangement and electrostatic bond reconstruction, which allows facile self-healing and reprocessing at room temperature to significantly extend the service lifetime of both products and raw materials. With higher water content, the dynamic electrostatic interactions and precipitation-dissolution equilibrium endow the QCS-SL bioplastic films with considerable solubility in water, which is promising to mitigate the plastic accumulation in aquatic environment. Because both QCS and SL are biocompatible and biodegradable, the dissolved QCS-SL films are nontoxic and environmentally friendly. Thus, this novel supramolecular bioplastic is highly sustainable throughout the whole life cycle, which is expected to open a new vista in sustainable plastic materials.

Comprehensive Review on the Impact of Chemical Composition, Plasma Treatment, and Vacuum Ultraviolet (VUV) Irradiation on the Electrical Properties of Organosilicate Films.

Organosilicate glass (OSG) films are a critical component in modern electronic devices, with their electrical properties playing a crucial role in device performance. This comprehensive review systematically examines the influence of chemical composition, vacuum ultraviolet (VUV) irradiation, and plasma treatment on the electrical properties of these films. Through an extensive survey of literature and experimental findings, we elucidate the intricate interplay between these factors and the resulting alterations in electrical conductivity, dielectric constant, and breakdown strength of OSG films. Key focus areas include the impact of diverse organic moieties incorporated into the silica matrix, the effects of VUV irradiation on film properties, and the modifications induced by various plasma treatment techniques. Furthermore, the underlying mechanisms governing these phenomena are discussed, shedding light on the complex molecular interactions and structural rearrangements occurring within OSG films under different environmental conditions. It is shown that phonon-assisted electron tunneling between adjacent neutral traps provides a more accurate description of charge transport in OSG low-k materials compared to the previously reported Fowler-Nordheim mechanism. Additionally, the quality of low-k materials significantly influences the behavior of leakage currents. Materials retaining residual porogens or adsorbed water on pore walls show electrical conductivity directly correlated with pore surface area and porosity. Conversely, porogen-free materials, developed by Urbanowicz, exhibit leakage currents that are independent of porosity. This underscores the critical importance of considering internal defects such as oxygen-deficient centers (ODC) or similar entities in understanding the electrical properties of these materials.

Ring Rearrangement Reactions of 4-Alkenylisocoumarins and Photophysical Evaluation of Multi-Substituted Anthracene Products.

Herein we report that readily available 4-alkenylisocoumarins can be regarded as potent dienolate equivalents. For example, lactol silyl ethers derived from 4-alkenylisocoumarins were selectively converted to the corresponding benzo-homophthalates through a fluoride-induced ring opening step that was followed by a ring closure through a vinylogous intramolecular aldol condensation. Likewise, nucleophilic activation of 4-alkenylisocoumarins directly yields diversely poly-substituted naphthalenes and anthracenes without formation of any regioisomer. Photophysical evaluation of a set of thus obtained 1,3-di- and 1,3,4-trisubstituted anthracenes reveals their distinct intramolecular charge transfer (ICT) character during light absorption in polar solutions and excimer emission from the solid state when a face-to-face π-stacked molecular assembly is present in the crystal packing.

Palladium‐Catalyzed Asymmetric Allylic Substitutions Achieved by C–N Axially Chiral N‐Arylpyrrole Derived Monophosphine Ligands

Monophosphine ligands based on C–N axially chiral N‐Arylpyrrole backbones are prepared starting from amino acids and evaluated in Pd‐catalyzed asymmetric allylic substitutions. 20.7‐ 99.9% ees are achieved in the reactions of rac‐1,3‐diphenylallyl acetates with O‐, N‐ and C‐nucleophiles. Ligand screening revealed that the steric hindrance from 3‐ or 4‐ position of the pyrrole is crucial for the enantioselectivity of the reaction. The synthetic utilization of the products was demonstrated by the transformation of one product by a gold‐catalyzed oxidative rearrangement reaction.

Effect of TiO₂ Addition on Elastic Moduli, Optical Bandgap, and Electrical Conductivity of xTiO₂-(0.30-x)Bi₂O₃-0.10ZnO-0.60TeO₂ Glassy Systems with Improved Thermal Stability

Glassy systems with the chemical composition xTiO2-(0.30-x)Bi2O3-0.10ZnO-0.60TeO2 (x = 0.05,0.10,0.15,0.20) have been synthesized using the melt quench approach. Numerous physical, electrical, optical, and other features of elastic moduli have been evaluated as titanium oxide concentration rises. The amorphous properties of the materials under inspection are displayed in the XRD pattern. As the concentration of arsenic rises, the glasses' density falls from 4.18 to 3.96 g/cm3, while their molar volume rises from 48.21 to 53.06 cm3mol-1. The elastic properties of the synthesized glasses, such as the shear (S) and longitudinal (L) stresses, bulk modulus (K), Young's modulus (Y), and Poisson's ratio (Pr), have all been measured using the measured values of the ultrasonic velocities. The increase in elastic moduli values showed that the materials' elastic qualities have been improved. The results are explained in terms of a significant structural alteration caused by molecular rearrangement, which controls the physical properties of the glass. The addition of titanium oxide is shown to cause a decrease in Urbach energies from 0.96 to 0.67 eV, which results in an increase in the optical band gap energies from 2.96 to 3.33 eV. DSC thermogram measurements reveal mechanically enhanced and thermally stable materials with potential for use in semiconducting devices.

Elastic Moduli, and Estimations of Some Physical, Thermal, and Optical Parameters of Ge-Se-As Glassy Systems with Improved Mechanical Strength

Employing the melt quench approach, glassy systems with the chemical composition Ge30Se(70-x)Asx have been synthesized. As the amount of arsenic increases, various physical, mechanical, thermal, optical parameters and some other aspects of elastic moduli have been assessed. The XRD pattern shows the amorphous characteristics of the inspected materials. The density of the glasses increases from 4.32 to 4.61 g-cm-3 whereas the molar volume declines from 19.32 to 18.62 cm3 mol-1 as the concentration of arsenic increases. The measured values of the ultrasonic velocities have been used to measure the elastic properties, such as the Shear, and longitudinal strains, Bulk modulus, Young's modulus, and Poisson's ratio of the synthesized glasses. The upsurge in the values of elastic moduli indicated the upgrading in the elastic properties of the materials. The outcomes are interpreted in terms of a profound structural change brought about by molecular rearrangement, which regulates the glass’s physical characteristics. The optical band gap energies are found to decrease from 2.17 to 1.86 eV due to the increase in Urbach energies from 040 to 0.64 eV with the incorporation of arsenic atom. The obtained results indicate the perspective of the as-synthesized thermally stable materials to be used in optoelectronic devices.

Agrocybe cylindracea Dietary Fiber Modification: Sodium Hydroxide Treatment Outperforms High-Temperature, Cellulase, and Lactobacillus Fermentation.

Agrocybe cylindracea dietary fiber (ADF) contains 95% water-insoluble dietary fiber, resulting in poor application performance. To address this issue, ADF was modified by four methods (cellulase, sodium hydroxide, high-temperature, and Lactobacillus fermentation) in this paper. By comparing the physicochemical properties, microstructures, monosaccharide compositions, and functional characteristics (antioxidant and α-glucosidase inhibitory activities in vitro) of all modified ADF samples, the optimal modification method was selected. Results showed that sodium hydroxide treatment was deemed the most effective modification method for ADF, as alkali-treated ADF (ADF-A) revealed a higher oil-holding capacity (2.02 g/g), swelling capacity (8.38 mL/g), cholesterol adsorption (6.79 mg/g), and α-glucosidase inhibitory activity (more than 70% at 0.4-0.6 mg/mL) than the other modified samples. The looser microstructure in ADF-A might be attributed to molecular rearrangement and spatial structure disruption, which resulted in smaller molecular sizes and decreased viscosity, hence improving ADF's physicochemical and functional qualities. All these findings indicate the greater application potential of modified ADF products in food and weight-loss industries, providing a comprehensive reference for the industrial application of ADF.

Recent synthetic strategies for N-arylation of pyrrolidines: a potential template for biologically active molecules.

The chemistry of nitrogen-containing heterocyclic compounds has been a multifaceted area of research for an extended period due to their varied therapeutic and biological significance. N-Aryl pyrrolidine formed by condensation of aryl group with nitrogen atom of pyrrolidine is present in a wide array of compounds. Various significant activities shown by N-arylated pyrrolidine include anti-Alzheimer, antihypoxic, anticancer, plant activator, analgesic effect, and hepatitis C inhibitor. This review summarizes different synthetic approaches, e.g., transition-metal catalyzed and transition-metal-free synthesis, decarboxylation reaction, reductive amination, nucleophilic cyclization, Ullmann-Goldberg amidation, Buchwald-Hartwig reaction, Chan-Evans-Lam coupling, addition to benzyne, multistep reaction, green synthesis, rearrangement reaction, and multicomponent reaction, to afford the derivatives of N-aryl pyrrolidine. It encompasses synthetic strategies documented from 2015 to 2023.

Ultrasonication: An Efficient Alternative for the Physical Modification of Starches, Flours and Grains.

Ultrasonic (USC) treatments have been applied to starches, flours and grains to modify their physicochemical properties and improve their industrial applicability. The extent of the modification caused by USC treatment depends on the treatment conditions and the natural characteristics of the treated matter. Cavitation leads to structural damage and fragmentation and partial depolymerization of starch components. The amorphous regions are more susceptible to being disrupted by ultrasonication, while the crystalline regions require extended USC exposure to be affected. The increased surface area in USC-treated samples has a higher interaction with water, resulting in modification of the swelling power, solubility, apparent viscosity, pasting properties and gel rheological and textural properties. Starch digestibility has been reported to be modified by ultrasonication to different extents depending on the power applied. The most important treatment variables leading to more pronounced modifications in USC treatments are the botanical origin of the treated matter, USC power, time, concentration and temperature. The interaction between these factors also has a significant impact on the damage caused by the treatment. The molecular rearrangement and destruction of starch structures occur simultaneously during the USC treatment and the final properties of the modified matrix will depend on the array of treatment parameters. This review summarizes the known effects of ultrasonic treatments in modifying starches, flours and grains.

Polydimethylsiloxane enabled triple-action water-resistant coating with desirable relaxation rate in clear aligner

Clear aligners undergo rapid stress relaxation in warm, moist oral environments, compromising therapeutic effectiveness and longevity of treatment. To develop an innovative multilayer composite material with improved stability and reduced stress release, we have engineered an innovative coating characterized by the surface aggregation of polydimethylsiloxane (PDMS), which imparts a pronounced hydrophobic effect. In addition, the chemically and physically cross-linked structure of the coating reduces the free volume created by molecular chain rearrangement owing to the presence of water molecules, thereby minimizing water penetration into the coating. Concurrently, the coating’s internal structure is enriched with numerous polar functional groups to capture water molecules that penetrate into the inside of the coating. Through combination of these mechanisms, water molecules are effectively sequestered, thereby impeding their penetration into the polyethylene terephthalate glycol (PETG) substrate. The impact of the polydimethylsiloxane content on the triple-action water-resistance mechanisms was thoroughly examined using attenuated total reflection (ATR)-Fourier transform infrared (FTIR), water absorption rate, water swelling rate, and X-ray photoelectron spectroscopy. The low surface energy cross-linked polyurethane coating is applied to the polyethylene terephthalate glycol (PETG) substrate to create a novel composite material with specific mechanical properties and reduced stress relaxation. The composite material remains stable in simulated oral environment with linear swelling rate of 0.58 % upon water absorption. Additionally, the stress release rate of the composite material within 336 h is notably lower (23.64 %) than that of PETG (62.29 %).