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The scientific community needs to conduct research on novel electrodes for portable energy storage (PES) devices like supercapacitors (S-Cs) and lithium-ion batteries (Li-ion-Bs) to overcome energy crises, especially in rural areas where no electrical poles are available. Herein, the nanostructured MoS2 and ZnS-MoS2 E-Ms consisting of nanoparticles/rods/sheets (N-Ps-Rs-Ss) are deposited on hierarchical nickel foam by a homemade chemical vapor deposition (H-M CVD) route. The X-ray diffraction patterns confirm the formation of polycrystalline films growing along various orientations, whereas the field-emission scanning electron microscope analysis confirms the formation of N-Ps-Rs-Ss. The change in structural and microstructural parameters indicates the existence of defects improving the energy storage ability of the deposited ZnS-MoS2@Ni-F electrodes. The specific capacitances of MoS2@Ni-F and ZnS-MoS2@Ni-F electrodes are found to be 1763 and 3565 F/g at 0.5 mV/s and 1451 and 3032 F/g at 1 A/g, respectively. The growing behavior of impedance graphs indicates their capacitive nature; however, the shifting of impedance curves toward y-axis indicates that the increasing diffusion rates due to the formation of nanostructures of ZnS-MoS2 results in low impedance. An excellent energy storage performance, minimum capacity fading, and improved electrical conductivity of the deposited E-Ms are due to the combined contributions of the electrical double layer and pseudocapacitor nature, which is again confirmed by theoretical Dunn's model. The absence of charge transfer resistance and good capacitance retention (95%) even after 10,000 cycles indicates that the deposited E-Ms are better for PES devices like S-Cs and Li-ion-Bs than MoS2 E-Ms. The assembled asymmetric supercapacitor device exhibited the maximum specific capacitance = 996 F/g, energy density = 354-285 W h/kg, power density = 2400-24,000 W/kg, capacitance retention = 95% and Coulombic efficiency = 100% even after a long charging-discharging of 10,000 cycles.
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The intestine of living organisms harbors different microbiota associated with the biological functioning and health of the host and influences the process of ecological adaptation. Here, we studied the intestinal microbiota's composition and functional differences using 16S rRNA and metagenomic analysis in the wild, farm, and released Chinese three-keeled pond turtle (Mauremys reevesii). At the phylum level, Bacteroidota dominated, followed by Firmicutes, Fusobacteriota, and Actinobacteriota in the wild group, but Chloroflexi was more abundant in the farm and released groups. Moreover, Chryseobacterium, Acinetobacter, Comamonas, Sphingobacterium, and Rhodobacter were abundant in the released and farm cohorts, respectively. Cetobacterium, Paraclostridium, Lysobacter, and Leucobacter showed an abundance in the wild group. The Kyoto Encyclopedia of Genes and Genomes (KEGG) database revealed that the relative abundance of most pathways was significantly higher in the wild turtles (carbohydrate metabolism, lipid metabolism, metabolism of cofactors, and vitamins). The comprehensive antibiotic resistance database (CARD) showed that the antibiotic resistance gene (ARG) subtype macB was the most abundant in the farm turtle group, while tetA was higher in the wild turtles, and srpYmcr was higher in the released group. Our findings shed light on the association between the intestinal microbiota of M. reevesii and its habitats and could be useful for tracking habitats to protect and conserve this endangered species.
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Butyl paraben (BuP) is widely used in cosmetics, drugs, and food preservation. Recently it is an identified new pollutant that affects various aspects of reproduction, lipid metabolism, and nervous system. Behavioral activity serves as a pre-warning biomarker for predicting water quality. So, in this study, the changes in some behaviors and its neurotransmitters and cell apoptosis in the brain of Chinese striped-necked turtles (Mauremys sinensis) were studied when the turtles were exposed to BuP concentrations of 0, 5, 50, 500, and 5000 µg/L for 21 weeks. The results showed that, the basking time and altering scores to external stimuli in the groups of 50, 500, and 5000 µg/L were significantly reduced, while the time for body-righting was significantly increased, compared with the control (0 µg/L), indicating that the turtles exhibited depression and inactive behavior. The analysis of neurotransmitter in the brain showed that 5-hydroxytryptamine (5-HT) contents in the groups of 500 and 5000 µg/L were significantly higher than the other groups, which was due to an increase in the mRNA relative expression levels of the 5-HT receptor gene (5-HTR), neurotransmitter transporter genes (Drd4, Slc6a4), and neurotransmitter synthase tryptophan hydroxylase (TPH). Furthermore, GABA transaminase (GABA-T) activity increased in the 500 and 5000 µg/L groups, and tyrosine hydroxylase (TH) activity increased dramatically in the 5000 µg/L group. However, acetyl-CoA (AChE) activity was significantly reduced in these four BuP exposure groups. These changes could be attributed to decreased movement velocity and increased inactivity. Meanwhile, the mRNA expression level of BAX, Bcl-2, caspase-9 and TUNEL assay indicated the occurrence of cell apoptosis in the brains of the higher BuP exposed groups, which may play an important role in neuronal death inducing behavior change. In summary, these findings offer fundamental insights into turtle ecotoxicology and serve as a foundation for a comprehensive assessment of the ecological and health risks associated with BuP.
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Tortugas , Contaminantes Químicos del Agua , Animales , Tortugas/genética , Tortugas/metabolismo , Parabenos/metabolismo , Contaminantes Químicos del Agua/toxicidad , ARN Mensajero/metabolismo , Neurotransmisores/metabolismo , ChinaRESUMEN
Heavy metals are among the most ubiquitous environmental pollutants of recent decades. Copper is commonly used to control algal blooms or macrophyte and waste infestations, its ambient concentration has increased significantly, indicating possible environmental risk. To investigate the effects of copper exposure on bioaccumulation, antioxidant defense, immune response, and apoptosis in the Chinese Striped-necked Turtle Mauremys sinensis, three experimental groups, control (0.0 mg/L), Cu2 (2 mg/L) and Cu4 (4 mg/L) were designed, and sampled at 14 and 28 days. Results showed that copper accumulates in different organs depending on the concentration and exposure time, Liver > Kidney > Gut > Heart > Brain > Muscle and the time order was 28 days > 14 days. The liver enzymes AST, ALT, and ALP decreased when the turtles were exposed to copper stress, while the contents of bilirubin TBIL, DBIL, IBIL, and LDH showed a significant upward trend. Similarly, the mRNA expression level of acetylcholinesterase AChE in the brain was significantly downregulated upon copper exposure. An upward trend was noticed in the liver Metallothionein MT mRNA expression levels compared to the control group. The mRNA expression levels of antioxidant enzymes CAT, SOD, MnSOD, and GSH-PX1 in the liver increased initially and then significantly decreased. Furthermore, the relative mRNA expression levels of inflammatory cytokines IL-1ß, IL-8, TNF-α, and IFN-γ involved in inflammatory response significantly upregulated. Copper significantly increased the hepatic mRNA transcription of heat shock proteins HSP70 and HSP90 at different exposure durations. In addition, the relative mRNA levels of caspase3, caspase8, and caspase9 related to the caspase-dependent apoptotic pathway significantly increased under copper stress. These results explain that copper toxicity causes bioaccumulation, promotes oxidative stress, obstructs immunity, and induces inflammation and apoptosis by altering their gene expression levels in M. sinensis.
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Metallic nanowires (NWs) and their different compounds display incredible prospects for their use in various applications including media storage, sensor and solar cell devices along with the biological drug delivery systems. In this research work, the metallic NWs like nickel nanowires (Ni-NWs) are synthesized successfully by employing electrodeposition process. Anodic aluminum oxide (AAO) templates are employed as a platform with copper metal coating which acts as an active cathode. The synthesized Ni-NWs are examined through various characterization techniques including X-ray diffraction (XRD), scanning electron microscope (SEM) and vibrating sample magnetometer (VSM) to study the crystal structure, surface morphology and magnetic properties, respectively. The XRD analysis shows the development of various diffraction planes like Ni (111), Ni (200), Ni (220) which confirms the formation of polycrystalline nickel NWs. The SEM analysis reveals that the range of diameter and length of nickel NWs are found to be â¼160 to 200 and â¼4 to 11 micron respectively showing high aspect ratio (ranged from â¼200 to 300). The ferromagnetic behavior of Ni-NWs is confirmed by the hysteresis loop carried out for parallel and perpendicular configurations having Hc = 100 and 206 Oe, respectively. The obtained results suggest that the synthesized Ni- NWs may be used for high-density media storage devices.
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In aquatic organisms, ammonia is one of the major factors that affect energy levels when it exceeds its optimal concentration. Numerous studies have examined the effects of ammonia on aquatic animals, but its effect on metabolism is still unknown. The effect of ammonia on carbohydrates and lipid metabolism in the Chinese striped neck turtle (Mauremys sinensis) was investigated in this study by exposing the turtle to two different ammonia concentrations (A100: 1.53 mg L-1) and (A200: 2.98 mg L-1) for 24 and 48 h, respectively. Our results showed that the mRNA expression of adenosine monophosphate-activated protein kinase α1 (AMPKα1) significantly increased only in A100 at 24 h, whereas its activity increased in both ammonia-exposed groups. The two AMPK-regulated transcription factors responsible for carbohydrate metabolism also exhibited changes in ammonia-treated groups, as hepatocyte nuclear factor-4-alpha (HNF4α) increased and forkhead box protein O1 (FoxO1) decreased. The expression of phosphofructokinase (PFK) and glucose-6-phosphatase (G-6-PAS) was subsequently downregulated. In addition, transcription factors, carbohydrate-responsive element-binding protein (ChREBP), and sterol regulatory element-binding protein 1c (SREBP-1c), which are known to be involved in lipogenesis, were suppressed. These downstream genes include fatty acid synthase, stearoyl CoA desaturase, and acetyl-CoA carboxylase (FAS, SCD-1 and ACC). Moreover, the glucose content decreased, whereas the triglyceride content increased significantly in A200 at 24 h. We concluded that AMPK signaling inhibits gluconeogenesis and lipogenesis, and promotes glycolysis to meet energy demand under stressful conditions in M. sinensis.
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Metabolismo de los Lípidos , Tortugas , Animales , Proteínas Quinasas Activadas por AMP/genética , Proteínas Quinasas Activadas por AMP/metabolismo , Tortugas/metabolismo , Amoníaco/toxicidad , Amoníaco/metabolismo , Hígado/metabolismo , Proteína 1 de Unión a los Elementos Reguladores de Esteroles/genética , Glucosa/metabolismo , ChinaRESUMEN
Bimetallic nanostructures composited with carbonaceous materials are the potential contenders for quantitative glucose measurement owing to their unique nanostructures, high biomimetic activity, synergistic effects, good conductivity and chemical stability. In the present work, chemical vapors deposition technique has been employed to grow 3D carbon nanocoils (CNCs) with a chiral morphology on hierarchical macroporous nickel foam (NF) to get a CNCs/NF scaffold. Following, bimetallic Cu@Ni core-shell nanoparticles (CSNPs) are effectively coupled with this scaffold through a facile solvothermal route in order to fabricate a binder-free novel Cu@Ni CSNPs/CNCs/NF hybrid nanostructure. The constructed free-standing 3D hierarchical composite electrode guarantees highly efficient glucose redox activity due to core-shell synergistic effects, enhanced electrochemical active surface area, excellent electrochemical stability, improved conductivity with better ion diffusivity and accelerated reaction kinetics. Being a non-enzymatic glucose sensor, this electrode achieves highly swift response time of 0.1 s, ultra-high sensitivity of 6905 µA mM-1 cm-2, low limit of detection of 0.03 µM along with potential selectivity and good storage stability. Moreover, the proposed sensor is also tested successfully for the determination of glucose concentration in human serum samples under good recovery ranging from 96.6 to 102.1 %. The 3D Cu@Ni CSNPs/CNCs/NF composite electrode with unprecedented catalytic performance can be utilized as an ideal biomimetic catalyst in the field of non-enzymatic glucose sensing.
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Nanopartículas , Níquel , Carbono , Técnicas Electroquímicas/métodos , Electrodos , Glucosa , Humanos , Níquel/químicaRESUMEN
The first Pd-catalyzed asymmetric three-component reaction of 2,3-allenol, aryl iodides, and 2-arylmethylenemolononitriles has been developed via an allenol carbopalladation and an allylic cycloaddition cascade. This process allows rapid access to substituted tetrahydrofurans bearing diverse functional groups in good yields with high diastereoselectivities and excellent enantioselectivities. The concise total synthesis of a lignan, (-)-2-episesaminone, has been achieved by the elaboration of a functionalized tetrahydrofuran obtained from this reaction.
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This work presents a wideband, all-side square-cut square patch multiple-input, multiple-output circularly-polarized (MIMO-CP) high-isolation antenna. The MIMO-CP antenna contains a two-port square cut on all corners of the square patch, and parasitic elements of 9 × 5 periodic square metallic plates are designed and operated. The outer dimensions of the antenna are 40 × 70 mm2, and the FR4 substrate height is 1.6 mm. The proposed antenna with the parasitic elements improves impedance matching and enhances S-parameters and axial ratio (AR). In the suggested MIMO-CP antenna, a parasitic element is designed and placed around the antenna periodically to reduce mutual coupling (MC) and improve CP. Simulated results show that the suggested antenna has a wide bandwidth (BW) from 4.89 to 6.85 GHz for S11 and was < −10 dB with AR ≤ 3 dB from 5.42 to 6.58 GHz, with a peak gain of 6.6 dB. The suggested antennas have more than 30 dB isolation and a low profile, are affordable, easily made, and are CP. To make a comparison with the measured and simulated results, a MIMO-CP antenna structure was fabricated and tested. The suggested antenna is better in terms of efficiency, envelope correlation coefficient (ECC), diversity gain (DG), channel capacity loss (CCL), and total active reflection coefficient (TARC). The proposed antenna is adequate for WLAN applications.
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Bangladesh govt. launched a nationwide vaccination drive against SARS-CoV-2 infection from early February 2021. The objectives of this study were to evaluate the acceptance of the COVID-19 vaccines and examine the factors associated with the acceptance in Bangladesh. In between January 30 to February 6, 2021, we conducted a web-based anonymous cross-sectional survey among the Bangladeshi general population. At the start of the survey, there was a detailed consent section that explained the study's intent, the types of questions we would ask, the anonymity of the study, and the study's voluntary nature. The survey only continued when a respondent consented, and the answers were provided by the respondents themselves. The multivariate logistic regression was used to identify the factors that influence the acceptance of the COVID-19 vaccination. A total of 605 eligible respondents took part in this survey (population size 1630046161 and required sample size 591) with an age range of 18 to 100. A large proportion of the respondents are aged less than 50 (82%) and male (62.15%). The majority of the respondents live in urban areas (60.83%). A total of 61.16% (370/605) of the respondents were willing to accept/take the COVID-19 vaccine. Among the accepted group, only 35.14% showed the willingness to take the COVID-19 vaccine immediately, while 64.86% would delay the vaccination until they are confirmed about the vaccine's efficacy and safety or COVID-19 becomes deadlier in Bangladesh. The regression results showed age, gender, location (urban/rural), level of education, income, perceived risk of being infected with COVID-19 in the future, perceived severity of infection, having previous vaccination experience after age 18, having higher knowledge about COVID-19 and vaccination were significantly associated with the acceptance of COVID-19 vaccines. The research reported a high prevalence of COVID-19 vaccine refusal and hesitancy in Bangladesh. To diminish the vaccine hesitancy and increase the uptake, the policymakers need to design a well-researched immunization strategy to remove the vaccination barriers. To improve vaccine acceptance among people, false rumors and misconceptions about the COVID-19 vaccines must be dispelled (especially on the internet) and people must be exposed to the actual scientific facts.
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Actitud Frente a la Salud , Vacunas contra la COVID-19 , COVID-19/psicología , Adulto , Bangladesh/epidemiología , COVID-19/epidemiología , Estudios Transversales , Cultura , Femenino , Humanos , Masculino , Persona de Mediana Edad , Encuestas y Cuestionarios , Negativa a la VacunaciónRESUMEN
Ammonia is one of major pollutants in aquatic environment that induces severe stress and toxicity to organisms in aquatic system. The intestine acts a major defense line that protects living organisms from biotic and abiotic stresses. In the current study, we examined the effects of ammonia on intestinal histomorphology, transcriptional levels of intestinal barrier functioning genes and intestinal microbiota of Chinese striped-neck turtle (Mauremys sinensis). Thus, the turtles were placed in water with addition of ammonia at 0 (control), 100, 200 mg L-1 for 30 days. Our findings showed that ammonia reduced the villus length and induced the inflammatory cells appearance. In addition, the epithelial tight junction genes, claudin and zonola occludin significantly downregulated in ammonia exposed groups as compared to control group (P < 0.05). Similarly, the mRNA expression levels of MUC-2 gene also significantly decreased in ammonia treated groups (P < 0.05). However, the expression levels of intestinal immune related genes such as IL-10, IL-12, TGF-ß1, TNF-α and IFN-γ significantly increased (P < 0.05). Furthermore, ammonia changed gut microbial diversity variedly. At the phylum levels, Firmicutes increased, whereas Bacteroidota, Desulfobacterota and Synergistota decreased significantly. Likewise, Lachnospiraceae, Bacteroides, Eubacteriaceae, Desulfovibrio, Muribaculaceae, Bilophila, Cloacibacillus, Christensenellaceae, Ruminococcus and Parabacteroides decreased while, Romboutsia and Turicibacter increased in ammonia exposed groups. In conclusion, ammonia at 100 and 200 mg L-1 could alter the intestinal barrier function and change the composition of intestinal microbiota, leading to bad health status in M. sinensis.
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Microbiota , Tortugas , Amoníaco/toxicidad , Animales , China , Mucosa IntestinalRESUMEN
In this study, amidoxime-functionalized silica decorated with copper (AFS-Cu) was fabricated and tested for its catalytic application. Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction were employed to characterize its structure and morphology. The application of AFS-Cu as a catalyst for the catalytic reduction of methylene blue (MB) in aqueous media using NaBH4 as reductant was evaluated. The ability to reuse as well as the effect of catalyst dose and pH of solution on the catalytic activity was investigated. The reduction of MB followed pseudo-first-order kinetics and the rate constant (k) was 0.6224 min-1. AFS-Cu was found to be a highly effective catalyst for MB reduction reaction and can be easily recovered and reused several times with no appreciable loss of catalytic activity.
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A new asymmetric catalytic protocol for the synthesis of enantioenriched N-allyl 2-pyrodones has been developed via the first Pd-catalyzed regio- and enantioselective aminoarylation of allenols with aryl iodides and 2-pyridones. By using a palladium complex generated in situ from Pd2(dba)3·CHCl3 and (S,S,S)-SKP as a catalyst, the three-component aminoarylation proceeded smoothly to afford a variety of functionalized N-allylic 2-pyridones in high yields with good regioselectivities and excellent enantioselectivities.
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The present research work was carried out to determine the bioaccumulation of manganese and chromium in the gills, intestine, muscles, skin and bones, as well as its acute toxicity and effects on hematological and biochemical parameters in Common carp (Cyprinus carpio). Adult carps were exposed for 96 h to manganese sulphate and chromium chloride solution, a sub lethal concentration was used in the experiment. Bioaccumulation was highest in the gills followed by intestine > muscles > skin > bones. The concentration of hematocrit (HCT) (37.3 ± 0.36), hemoglobin (HGB) (9.0 ± 0.04), Red Blood Cells (RBCs) (3.7 ± 0.025), mean corpuscular volume (MCV) (121.2 ± 0.36), mean corpuscular hemoglobin (MCH) (41.3 ± 0.3) and mean corpuscular hemoglobin concentration (MCHC) (41.06 ± 0.072) was significantly higher at 96 h (P < 0.01) after exposure to manganese and chromium, while the concentration of platelets (PLT) (16.8 ± 0.12) and white blood cells (WBCs) (62.7 ± 0.11) was lower at 96 h of exposure. Serum glutamic pyruvic transaminase (SGPT) (40.6 ± 0.4), Blood Urea (13 ± 0.1), serum triglycerides (231.21 ± 0.04), high-density lipoprotein (HDL) (39 ± 0.07), serum Alkaline PO4 (242 ± 0.2), lactate dehydrogenase (LDH) (1239 ± 13.21), and serum Uric Acid (4.81 ± 0.33) were significantly higher (P < 0.01) at 96 h of exposure. The highest concentration of serum cholesterol (339 ± 0.09), serum reatinine (0.9 ± 0.01), low density lipid (240 ± 0.2) was observed at 24 h. Serum glutamic-oxaloacetic transaminase (SGOT) (19 ± 0.13), and serum albumin were at the highest level at 72 h (3.19 ± 0.07) (P < 0.01) post exposure.
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Herein, a practical and efficient approach to tetrahydrofurans with three-stereocenters has been developed through Pd-catalyzed asymmetric allylic cycloaddition of vinylethylene carbonates (VECs) with 2-nitroacrylates under mild conditions. By using this asymmetric catalytic reaction as a key step, several furofuran lignans with stereodivergency have been effectively synthesized through 5- or 6-step sequences from readily available starting materials.
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BACKGROUND: Thrombotic thrombocytopenic purpura is an autoimmune disease that carries a high mortality. Very few case reports in the literature have described a relationship between Graves disease and thrombotic thrombocytopenic purpura. We present a case of a patient with Graves disease who was found to be biochemically and clinically hyperthyroid with concurrent thrombotic thrombocytopenic purpura. CASE PRESENTATION: Our patient was a 30-year-old African American woman with a history of hypertension and a family history of Graves disease who had recently been diagnosed with hyperthyroidism and placed on methimazole. She presented to our hospital with the complaints of progressive shortness of breath and dizziness. Her vital signs were stable. On further evaluation, she was diagnosed with thrombotic thrombocytopenic purpura, depending on clinical and laboratory results, and also was found to have highly elevated free T4 and suppressed thyroid-stimulating hormone. She received multiple sessions of plasmapheresis and ultimately had a total thyroidectomy. The patient's hospital course was complicated by pneumonia and acute respiratory distress syndrome. Her platelets stabilized at approximately 50,000/µl, and her ADAMTS13 activity normalized despite multiple complications. The patient ultimately had a cardiac arrest with pulseless electrical activity and died despite multiple attempts at cardiopulmonary resuscitation. CONCLUSION: Graves disease is an uncommon trigger for the development of thrombotic thrombocytopenic purpura, and very few cases have been reported thus far. Therefore, clinicians should be aware of this association in the appropriate clinical context to comprehensively monitor hyperthyroid patients during treatment.
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Enfermedad de Graves/complicaciones , Hipertensión/complicaciones , Púrpura Trombocitopénica Trombótica/diagnóstico , Adulto , Mareo , Disnea , Resultado Fatal , Femenino , Enfermedad de Graves/tratamiento farmacológico , Enfermedad de Graves/fisiopatología , Paro Cardíaco , Humanos , Hipertensión/fisiopatología , Plasmaféresis , Púrpura Trombocitopénica Trombótica/tratamiento farmacológico , Púrpura Trombocitopénica Trombótica/etiología , Púrpura Trombocitopénica Trombótica/fisiopatología , TiroidectomíaRESUMEN
An efficient method for the enantioselective synthesis of cyclic ureas has been developed through Pd-catalyzed asymmetric allylic cycloaddition of readily accessible nitrogen-containing allylic carbonates with isocyanates. By using a palladium complex in situ generated from Pd2(dba)3·CHCl3 and phosphoramidite L1 or L3 as a ligand under mild reaction conditions, the process afforded imidazolidinones and tetrahydropyrimidinones with high yields and high levels of enantioselectivities.
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A useful method for the enantioselective preparation of isoxazoline N-oxides via Pd-catalyzed asymmetric allylic cycloaddition of nitro-containing allylic carbonates has been developed. By using palladium complex in situ generated from Pd2(dba)3·CHCl3 and phosphoramidite L2 as a catalyst under mild conditions, the transformation afforded vinylated isoxazoline N-oxides in high yields with acceptably high enantioselectivities.
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An efficient method for the asymmetric synthesis of N-substituted 2-pyridones via Pd-catalyzed regio- and enantioselective allylic substitution of hydroxyl-containing allylic carbonates with 2-pyridones has been developed. By using a palladium complex in situ generated from Pd2(dba)3·CHCl3 and phosphoramidite L2 as a ligand, the process allowed rapid access to N-substituted 2-pyridones with complete chemo- and regioselectivities and good to high enantioselectivities.
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An efficient method for the construction of furanobenzodihydropyran skeletons has been developed through Pd-catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with 3-cyanochromones. By using a palladium complex generated in situ from [Pd2(dba)3]·CHCl3 and phosphoramidite L3 as a catalyst under mild reaction conditions, the process afforded furanobenzodihydropyrans bearing vicinal quaternary stereocenters in high yields with good to high enantio- and diastereoselectivities.