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An X-ray analysis of exfoliated MoS2, produced by means of microwave-assisted liquid-phase exfoliation (LPE) from bulk powder in 1-methyl-2-pyrrolidone (NMP) or acetonitrile (ACN) + 1-methyl-2-pyrrolidone (NMP) solvents, has revealed distinct structural differences between the bulk powder and the microwave-exfoliated samples. Specifically, we performed X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements to identify the elements of our exfoliated sample deposited on a Si substrate by drop-casting, as well as their chemical state and its structural crystalline phase. In the exfoliated sample, the peaks pattern only partially resemble the theoretical Miller indices for MoS2. In contrast, the bulk powder's spectrum shows the characteristic peaks of the 2H polytype of MoS2, but with some broadening. Notable is the retention of partial crystallinity in the post-exfoliation phases, specifically in the normal-to-plane orientation, thus demonstrating the effectiveness of microwave-assisted techniques in producing 2D MoS2 and attaining desirable properties for the material. XPS measurements confirm the success of the exfoliation procedure and that the exfoliated sample retains its original structure. The exfoliation process has been optimized to maintain the structural integrity of MoS2 while enhancing its surface area and electrochemical performance, thereby making it a promising material for advanced electronic and optoelectronic applications ranging from energy storage to sensing devices under ambient conditions. [ABSTRACT FROM AUTHOR]

Screen-printed electrodes (SPEs) are reliable, portable, affordable, and versatile electrochemical platforms for the real-time analytical monitoring of emerging analytes in the environmental, clinical, and agricultural fields. The aim of this study was to evaluate the electrochemical behavior of gold screen-printed electrodes (SPGEs) modified with molecules containing amino (Tr-N) or α-aminophosphonate (Tr-P) groups for the selective and sensitive detection of the toxic metal ions Pb2+ and Hg2+ in aqueous samples. After optimizing the analytical parameters (conditioning potential and time, deposition potential and time, pH and concentration of the supporting electrolyte), anodic square wave stripping voltammetry (SWASV) was used to evaluate and compare the electrochemical performance of bare or modified electrodes for the detection of Hg2+ and Pb2+, either alone or in their mixtures in the concentration range between 1 nM and 10 nM. A significative improvement in the detection ability of Pb2+ ions was recorded for the amino-functionalized gold sensor SPGE-N, while the presence of a phosphonate moiety in SPGE-P led to greater sensitivity towards Hg2+ ions. The developed sensors allow the detection of Pb2+ and Hg2+ with a limit of detection (LOD) of 0.41 nM and 35 pM, respectively, below the legal limits for these heavy metal ions in drinking water or food, while the sensitivity was 5.84 µA nM−1cm−2 and 10 µA nM−1cm−2, respectively, for Pb2+ and Hg2+. The reported results are promising for the development of advanced devices for the in situ and cost-effective monitoring of heavy metals, even in trace amounts, in water resources. [ABSTRACT FROM AUTHOR]

Potassium channels have recently emerged as suitable target for the treatment of epileptic diseases. Among potassium channels, KCNT1 channels are the most widely characterized as responsible for several epileptic and developmental encephalopathies. Nevertheless, the medicinal chemistry of KCNT1 blockers is underdeveloped so far. In the present review, we describe and analyse the papers addressing the issue of KCNT1 blockers' development and identification, also evidencing the pros and the cons of the scientific approaches therein described. After a short introduction describing the epileptic diseases and the structure–function of potassium channels, we provide an extensive overview of the chemotypes described so far as KCNT1 blockers, and the scientific approaches used for their identification. [ABSTRACT FROM AUTHOR]

The one-pot synthesis of N-doped graphene quantum dots (GQDs), capped with a positively charged polyamine (trien), has been realized through a microwave-assisted pyrolysis on solid L-glutamic acid and trien in equimolar amounts. The resulting positively charged nanoparticles are strongly emissive in aqueous solutions and are stable for months. The interaction with the anionic tetrakis(4-sulphonatophenyl)porphyrin (TPPS4) has been investigated at neutral and mild acidic pH using a combination of UV/vis absorption spectroscopy together with static and time-resolved fluorescence emission. At pH = 7, the experimental evidence points to the formation of a supramolecular adduct mainly stabilized by electrostatic interactions. The fluorescence emission of the porphyrin is substantially quenched while GQDs remain still emissive. On decreasing the pH, protonation of TPPS4 leads to formation of porphyrin J-aggregates through the intermediacy of the charged quantum dots. [ABSTRACT FROM AUTHOR]

Schiff bases (SBs) are important ligands in coordination chemistry due to their unique structural properties. Their ability to form complexes with metal ions has been exploited for the environmental detection of emerging water contaminants. In this work, we evaluated the complexation ability of three newly proposed SBs, 1–3, by complete conformational analysis, using a combination of Molecular Dynamics and Density Functional Theory studies, to understand their ability to coordinate toxic heavy metal (HMs) ions. From this study, it emerges that all the ligands present geometries that make them suitable to complex HMs through the N-imino moieties or, in the case of 3, with the support of the oxygen atoms of the ethylene diether chain. In particular, this ligand shows the most promising coordination behavior, particularly with Pb2+. [ABSTRACT FROM AUTHOR]

Solid tumors are a leading cause of cancer-related deaths globally, being characterized by rapid tumor growth and local and distant metastases. The failures encountered in cancer treatment are mainly related to the complicated biology of the tumor microenvironment. Nanoparticles-based (NPs) approaches have shown the potential to overcome the limitations caused by the pathophysiological features of solid cancers, enabling the development of multifunctional systems for cancer diagnosis and therapy and allowing effective inhibition of tumor growth. Among the different classes of NPs, 2D graphene-based nanomaterials (GBNs), due to their outstanding chemical and physical properties, easy surface multi-functionalization, near-infrared (NIR) light absorption and tunable biocompatibility, represent ideal nanoplatforms for the development of theranostic tools for the treatment of solid tumors. Here, we reviewed the most recent advances related to the synthesis of nano-systems based on graphene, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs), for the development of theranostic NPs to be used for photoacoustic imaging-guided photothermal–chemotherapy, photothermal (PTT) and photodynamic therapy (PDT), applied to solid tumors destruction. The advantages in using these nano-systems are here discussed for each class of GBNs, taking into consideration the different chemical properties and possibility of multi-functionalization, as well as biodistribution and toxicity aspects that represent a key challenge for their translation into clinical use. [ABSTRACT FROM AUTHOR]

Recently, we demonstrated that a Citrus flavanone mix (FM) shows antioxidant and anti-inflammatory activity, even after gastro-duodenal digestion (DFM). The aim of this study was to investigate the possible involvement of the cyclooxygenases (COXs) in the anti-inflammatory activity previously detected, using a human COX inhibitor screening assay, molecular modeling studies, and PGE2 release by Caco-2 cells stimulated with IL-1β and arachidonic acid. Furthermore, the ability to counteract pro-oxidative processes induced by IL-1β was evaluated by measuring four oxidative stress markers, namely, carbonylated proteins, thiobarbituric acid-reactive substances, reactive oxygen species, and reduced glutathione/oxidized glutathione ratio in Caco-2 cells. All flavonoids showed a strong inhibitory activity on COXs, confirmed by molecular modeling studies, with DFM, which showed the best and most synergistic activity on COX-2 (82.45% vs. 87.93% of nimesulide). These results were also corroborated by the cell-based assays. Indeed, DFM proves to be the most powerful anti-inflammatory and antioxidant agent reducing, synergistically and in a statistically significant manner (p < 0.05), PGE2 release than the oxidative stress markers, also with respect to the nimesulide and trolox used as reference compounds. This leads to the hypothesis that FM could be an excellent antioxidant and COX inhibitor candidate to counteract intestinal inflammation. [ABSTRACT FROM AUTHOR]

Cancer-targeted drug delivery systems (DDS) based on carbon nanostructures have shown great promise in cancer therapy due to their ability to selectively recognize specific receptors overexpressed in cancer cells. In this paper, we have explored a green route to synthesize nanobiochar (NBC) endowed with graphene structure from the hydrothermal carbonization (HTC) of orange peels and evaluated the suitability of this nanomaterial as a nanoplatform for cancer therapy. In order to compare the cancer-targeting ability of different widely used targeting ligands (TL), we have conjugated NBC with biotin, riboflavin, folic acid and hyaluronic acid and have tested, in vitro, their biocompatibility and uptake ability towards a human alveolar cancer cell line (A549 cells). The nanosystems which showed the best biological performances—namely, the biotin- and riboflavin- conjugated systems—have been loaded with the poorly water-soluble drug DHF (5,5-dimethyl-6a-phenyl-3-(trimethylsilyl)-6,6a-dihydrofuro[3,2-b]furan-2(5H)-one) and tested for their anticancer activity. The in vitro biological tests demonstrated the ability of both systems to internalize the drug in A549 cells. In particular, the biotin-functionalized NBC caused cell death percentages to more than double with respect to the drug alone. The reported results also highlight the positive effect of the presence of oxygen-containing functional groups, present on the NBC surface, to improve the water dispersion stability of the DDS and thus make the approach of using this nanomaterial as nanocarrier for poorly water-soluble drugs effective. [ABSTRACT FROM AUTHOR]

The last few years have increasingly emphasized the need to develop new active antiviral products obtained from artificial synthesis processes using nanomaterials, but also derived from natural matrices. At the same time, advanced computational approaches have found themselves fundamental in the repurposing of active therapeutics or for reducing the very long developing phases of new drugs discovery, which represents a real limitation, especially in the case of pandemics. The first part of the review is focused on the most innovative nanomaterials promising both in the field of therapeutic agents, as well as measures to control virus spread (i.e., innovative antiviral textiles). The second part of the review aims to show how computer-aided technologies can allow us to identify, in a rapid and therefore constantly updated way, plant-derived molecules (i.e., those included in terpenoids) potentially able to efficiently interact with SARS-CoV-2 cell penetration pathways. [ABSTRACT FROM AUTHOR]

Pure titanium and titanium alloys are widely used in dentistry and orthopedics. However, despite their outstanding mechanical and biological properties, implant failure mainly due to post-operative infection still remains a significant concern. The possibility to develop inherent antibacterial medical devices was here investigated by covalently inserting bioactive ammonium salts onto the surface of titanium metal substrates. Titanium discs have been functionalized with quaternary ammonium salts (QASs) and with oleic acid (OA), affording the Ti-AEMAC Ti-GTMAC, Ti-AUTEAB, and Ti-OA samples, which were characterized by ATR-FTIR and SEM-EDX analyses and investigated for the roughness and hydrophilic behavior. The chemical modifications were shown to deeply affect the surface properties of the metal substrates and, as a consequence, their bio-interaction. The bacterial adhesion tests against the Gram-negative Escherichia Coli and Gram-positive Staphylococcus aureus, at 1.5 and 24 h of bacterial contact, showed good anti-adhesion activity for Ti-AUTEAB and Ti-OA samples, containing a long alkyl chain between the silicon atom and the ammonium functionality. In particular, the Ti-AUTEAB sample showed inhibition of bacteria adhesion against Escherichia Coli of about one log with respect to the other samples, after 1.5 h. The results of this study highlight the importance of chemical functionalization in addressing the antimicrobial activity of metal surfaces and could open new perspectives in the development of inherent antibacterial medical devices. [ABSTRACT FROM AUTHOR]

The click cycloaddition of azides to alkynes affording 1,2,3‐triazoles is a widely used and effective chemical transformation, applied to obtain relevant products in medicine, biology, and materials science. In this work, a set of natural deep eutectic solvents (NADESs) has been investigated in the copper‐catalyzed azide‐alkyne cycloaddition reactions (CuAAc) as green and catalytic reaction media. The use of these innovative solvents has been shown to improve the reaction effectiveness, giving excellent yields. NADESs proved to be "active" in their reducing capabilities in several cases and for the absence of added bases in all the performed reactions: DFT calculations demonstrated in fact the involvement of H‐bonds between DESs and alkynes, as well as stabilization of copper catalytic intermediates. The green experimental conditions, the absence of a base, the low temperatures, the lowering of reagent amounts, and the possibility of recycling of the solvents, outline the great potential of NADESs for CuAAc. [ABSTRACT FROM AUTHOR]

The spread of SARS‐CoV‐2, along with the lack of targeted medicaments, encouraged research of existing drugs for repurposing. The rapid response to SARS‐CoV‐2 infection comprises a complex interaction of cytokine storm, endothelial dysfunction, inflammation, and pathologic coagulation. Thus, active molecules targeting multiple steps in SARS‐CoV‐2 lifecycle are highly wanted. Herein we explored the in silico capability of silibinin from Silybum marianum to interact with the SARS‐CoV‐2 main target proteins, and the in vitro effects against cytokine‐induced‐inflammation and dysfunction in human umbilical vein endothelial cells (HUVECs). Computational analysis revealed that silibinin forms a stable complex with SARS‐CoV‐2 spike protein RBD, has good negative binding affinity with Mpro, and interacts with many residues on the active site of Mpro, thus supporting its potentiality in inhibiting viral entry and replication. Moreover, HUVECs pretreatment with silibinin reduced TNF‐α‐induced gene expression of the proinflammatory genes IL‐6 and MCP‐1, as well as of PAI‐1, a critical factor in coagulopathy and thrombosis, and of ET‐1, a peptide involved in hemostatic vasoconstriction. Then, due to endothelium antiinflammatory and anticoagulant properties of silibinin and its capability to interact with SARS‐CoV‐2 main target proteins demonstrated herein, silibinin could be a strong candidate for COVID‐19 management from a multitarget perspective. [ABSTRACT FROM AUTHOR]

What is known and objective: Trimethylaminuria is a metabolic disorder characterized by excessive excretion of trimethylamine in body fluids following FMO3 gene mutations. Secondary forms of the disease may be due to consumption of trimethylamine precursor‐rich foods or metabolism of some xenobiotics. Case summary: A HIV patient developed secondary trimethylaminuria following antiretroviral treatment. Riboflavin supplementation ameliorated his phenotype. 1H‐NMR confirmed increased urine level of TMA. Several genes involved in choline catabolism harboured missense mutations. Riboflavin supplement improved enzymatic activity of mutated enzymes promoting TMA clearance. What is new and conclusion: Antiretrovirals may increase the concentration of TMA precursors. The present study reports antiretroviral treatment as risk factor for such secondary trimethylaminuria. Riboflavin is an effective treatment. [ABSTRACT FROM AUTHOR]

Aldose reductase (ALR2) is a key enzyme involved in diabetic complications and the search for new aldose reductase inhibitors (ARIs) is currently very important. The synthetic ARIs are often associated with deleterious side effects and medicinal and edible plants, containing compounds with aldose reductase inhibitory activity, could be useful for prevention and therapy of diabetic complications. Non-psychotropic phytocannabinoids exert multiple pharmacological effects with therapeutic potential in many diseases such as inflammation, cancer, diabetes. Here, we have investigated the inhibitory effects of extracts and their fractions from two Cannabis sativa L. chemotypes with high content of cannabidiol (CBD)/cannabidiolic acid (CBDA) and cannabigerol (CBG)/cannabigerolic acid (CBGA), respectively, on human recombinant and pig kidney aldose reductase activity in vitro . A molecular docking study was performed to evaluate the interaction of these cannabinoids with the active site of ALR2 compared to known ARIs. The extracts showed significant dose-dependent aldose reductase inhibitory activity (>70%) and higher than fractions. The inhibitory activity of the fractions was greater for acidic cannabinoid-rich fractions. Comparative molecular docking results have shown a higher stability of the ALR2-cannabinoid acids complex than the other inhibitors. The extracts of Cannabis with high content of non-psychotropic cannabinoids CBD/CBDA or CBG/CBGA significantly inhibit aldose reductase activity. These results may have some relevance for the possible use of C. sativa chemotypes based preparations as aldose reductase inhibitors. [ABSTRACT FROM AUTHOR]

A total of 205 bluefin and yellowfin tuna samples were examined for mercury detection in order to verify possible differences and have a detailed risk assessment of the two tuna species. The results showed significant higher mercury concentration in muscle tissue of bluefin tuna respect yellowfin tuna (p < 0.001) with mean concentration of 0.84 mg/kg and maximum value of 1.94 mg/kg. These differences can be due the different biological and ecological aspects of the two tuna species and to different oceanographic aspects between Atlantic Ocean and Mediterranean sea. The results obtained in this study suggest an advisable containment of the sources of pollution and further studies on the closed-loop farming of bluefin tuna, in order to ensure the product safety. [ABSTRACT FROM PUBLISHER]

A novel carbonylative approach to the synthesis of functionalized 1H-benzo[d]imidazo[1,2-a]imidazoles is presented. The method consists of the oxidative aminocarbonylation of N-substituted-1-(prop-2-yn-1-yl)-1H-benzo[d]imidazol-2-amines, carried out in the presence of secondary nucleophilic amines, to give the corresponding alkynylamide intermediates, followed by in situ conjugated addition and double-bond isomerization, to give 2-(1-alkyl-1H-benzo[d]imidazo[1,2-a]imidazol-2-yl)acetamides. Products were obtained in good to excellent yields (64-96%) and high turnover numbers (192-288 mol of product per mol of catalyst) under relatively mild conditions (100 °C under 20 atm of a 4:1 mixture of CO-air), using a simple catalytic system, consisting of PdI2 (0.33 mol %) in conjunction with KI (0.33 equiv). [ABSTRACT FROM AUTHOR]

The antioxidant activity and the phenolic and α-tocopherol content of 10 Northern Italian mono- and multi-varietal extra virgin olive oils (EVOOs), after early and late olive harvests, was analyzed. A hierarchical cluster analysis was used to evaluate sample similarity. Secoiridoids (SIDs), lignans and flavonoids were the most abundant phenolic compounds identified. The organic Casaliva (among mono-cultivar) and the organic multi-varietal (among blended oils) EVOOs had the higher total phenol content both in early (263.13 and 326.19 mg/kg, respectively) and late harvest (241.88 and 292.34 mg/kg, respectively) conditions. In comparison to late harvest EVOOs, early harvest EVOOs, in particular the organic mono-cultivar Casaliva, showed both higher antioxidant capacity (up to 1285.97 Oxygen Radicals Absorbance Capacity/ORAC units), probably due to the higher SID fraction (54% vs. 40%), and higher α-tocopherol content (up to 280.67 mg/kg). Overall, these results suggest that SIDs and α-tocopherol mainly contribute to antioxidant properties of the studied EVOOs. In light of this, the authors conclude that early harvest, organic mono-cultivar Casaliva EVOO represents the most interesting candidate to explicate healthy effects ascribed to these functional constituents, particularly regarding oxidative stress-related pathologies. [ABSTRACT FROM AUTHOR]

Coumarin is a natural compound well known for its phytotoxic potential. In the search for new herbicidal compounds to manage weeds, three synthetic derivatives bearing the coumarin scaffold (1-3), synthesized by a carbonylative organometallic approach, were in vitro assayed on germination and root growth of two noxious weeds, Amaranthus retroflexus and Echinochloa crus-galli. Moreover, the synthetic coumarins 1-3 were also in vitro assayed on seedlings growth of the model species Arabidopsis thaliana to identify the possible physiological targets. All molecules strongly affected seed germination and root growth of both weeds. Interestingly, the effects of synthetic coumarins on weed germination were higher than template natural coumarin, pointing out ED50 values ranging from 50-115 μM. Moreover, all synthetic coumarins showed a strong phytotoxic potential on both Arabidopsis shoot and root growth, causing a strong reduction in shoot fresh weight (ED50 values ≤ 60 μM), accompanied by leaf development and a decrease in pigment content. Furthermore, they caused a strong alteration in root growth (ED50 values ≤ 170 μM) and morphology with evident alterations in root tip anatomy. Taken together, our results highlight the promising potential herbicidal activity of these compounds. [ABSTRACT FROM AUTHOR]

A novel series of C-nucleosides, featuring the presence of a 1,2,3-triazole ring linked to an isoxazolidine system, has been designed as mimetics of the pyrimidine nucleobases. An antiproliferative effect was observed for compounds 17a and 17b: the growth inhibitory effect reaches the 50% in HepG2 and HT-29 cells and increases up to 56% in the SH-SY5Y cell line after 72 h of incubation at a 100 μM concentration. [ABSTRACT FROM AUTHOR]

5-Triazolyl-2-methylisoxazolidin-3-yl 3-phosphonates have been synthesized by 1,3-dipolar cycloaddition of N-methyl-C-diethoxyphosphorylnitrone and vinyl triazoles. The process showed a complete regioselectivity and a nearly exclusive cis stereoselectivity. M062X/6-31G(d,p) calculations rationalize the regio- and the stereochemical results. The formation of a hydrogen bond along a particular reaction channel significantly stabilizes both transition states and products related to cis-adducts. Biological tests indicate that the obtained compounds do not show relevant antiviral and anticancer activity. [ABSTRACT FROM AUTHOR]

New calix[4]arene conjugates that present polycyclic aromatic hydrocarbons (PAHs) at their exo rims have been synthesized by esterification of a cone-shaped calix[4]arenedicarboxylic acid with trans- or cis-pyrenylisoxazolidinyl alcohols prepared by a 1,3-dipolar cycloaddition methodology. The in vitro cytotoxic activities of all compounds were evaluated with three different human tumor cell lines, and the most potent one reached an IC50 of 95 n M. The different biological activities of the synthesized compounds were explained by docking and circular dichroism studies, which evidenced their intercalating abilities from the DNA minor groove. [ABSTRACT FROM AUTHOR]

1,2,3-Triazole-appended N,O-nucleosides have been synthesized by an approach combining a 1,3-dipolar cycloaddition process and an alkyne-azide click chemistry reaction. Biological assays, performed on six tumor cell lines, revealed the antiproliferative activity of the synthesized compounds. The effect was more evident in the U87MG human glioblastoma cell line. Thus, these nucleoside analogues could be promising scaffolds for the construction of new anticancer agents. [ABSTRACT FROM AUTHOR]

Starting from enantiomeric pure 1-[(3S,5R)- and 1-[(3R,5S)-3-(hydroxymethyl)- 2-methylisoxazolidin-5-yl]-5-methylpyrimidine-2,4(1H,3H)-diones (-)7a and (+)7b, obtained by lipase-catalyzed resolution, pure diethyl{[(3S,5R)-2-methyl-5-(5-methyl-2,4-dioxo-3,4- dihydropyrimidin-1(2H)-yl)isoxazolidin-3-yl]methyl}phosphonate (-)12a and diethyl{[(3R,5S)- 2-methyl-5-(5-methyl-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl)isoxazolidin-3-yl]methyl} phosphonate (+)12b have been synthesized. The obtained compounds showed no cytotoxic activity versus the U937 cell line in comparison with AZT, and were poorly able to inhibit HIV infection in vitro. [ABSTRACT FROM AUTHOR]

1-Indanones have been successfully prepared by means of three different non-conventional techniques, namely microwaves, high-intensity ultrasound and a Q-tube™ reactor. A library of differently substituted 1-indanones has been prepared via one-pot intramolecular Friedel-Crafts acylation and their efficiency and "greenness" have been compared. [ABSTRACT FROM AUTHOR]

This review offers an overview of the synthesis of phosphonated isoxazolidinyl nucleosides, a new class of interesting and potentially antiviral/antitumor agents. The synthetic methodology relies on a 1,3-dipolar cycloaddition reaction as a key step. The cycloaddition process involves substituted nitrones, phosphonated nitrones, or nitrones containing functional groups easily convertible into a phosphonated group. Biological assays are presented, which show that phosphonated isoxazolidinyl nucleosides represent a new promising template of nucleoside analogues. [ABSTRACT FROM AUTHOR]

Selective reductions of semicyclic imides either to hemiaminals ( endo carbonyl reduction) or to aldehydes and amines ( exo carbonyl reduction) in high yields by Schwartz's reagent (Cp2ZrHCl) are reported. Mechanistic aspects of these reactions have been investigated at the DFT ab initio level with consideration of implicit solvent effects and thermal and pressure corrections to 298 K/1 atm. The reactions proceed from the reagents to very stable final Zr-oxo intermediates through the formation of σ complexes and subsequent four-center transition state structures (1,2-migratory insertion). The energetic barriers for the insertion steps depend strongly on the natures of the ancillary groups at the reducing carbonyl groups. N-Carbamoyl groups are reduced to hemiaminals whereas N-acyl groups react at the exo carbonyl groups. The absence of the second carbonyl group in the simple N-methyl-2-pyrrolidone (less oxidized system) strongly reduces the thermodynamic drive for the formation of the metallocene oxo intermediate and allows an explanation of the remarkable chemoselectivity of the hydrozirconation. The zirconocene-oxo intermediates hydrolyze quickly throughout an ionic mechanism in which water molecules strongly assist the process by stabilizing ion pair separation. The computational results are consistent with a large set of experimental data on reduction of γ-lactam and isoxazolidinone derivatives under mild conditions. They provide a way to explain and predict the relative importance of the two competitive endo/ exo reduction channels of semicyclic imides by considering the electronic and steric features of substituents. [ABSTRACT FROM AUTHOR]

A novel rearrangement pathway of 3-alkoxycarbonyl-4-carbamoylisoxazolidines, leading to 1H-pyrrole-2,5-diones by treatment with TBAF, is reported. DFT quantum chemical calculations support the reaction route, controlled by ring strain, which proceeds through the opening of a bicyclic intermediate, with aldehyde extrusion. [ABSTRACT FROM AUTHOR]