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The oxidation of benzylic alcohols is an important transformation in modern organic synthesis. A plethora of photoredox protocols have been developed to achieve the aerobic oxidation of alcohols into carbonyls. Recently, several groups described that ultraviolet (UV) or purple light can initiate the aerobic oxidation of benzylic alcohols in the absence of an external catalyst, and depicted different mechanisms involving the photoinduction of â¢O2- as a critical reactive oxygen species (ROS). However, based on comprehensive mechanistic investigations, including control experiments, radical quenching experiments, EPR studies, UV-vis spectroscopy, kinetics studies, and density functional theory calculations (DFT), we elucidate here that HOOâ¢, which is released via the H2O2 elimination of α-hydroxyl peroxyl radicals [ArCR(OH)OOâ¢], serves as the real chain carrier for the autocatalytic photooxidation of benzylic alcohols. The mechanistic ambiguities depicted in the precedent literature are clarified, in terms of the crucial ROS and its evolution, the rate-limiting step, and the primary radical cascade. This work highlights the necessity of stricter mechanistic analyses on UV-driven oxidative reactions that involve aldehydes' (or ketones) generation.
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By increasing the number of modes of transmission in optical fiber, the mode-division multiplexing (MDM) technology can effectively improve the transmission capacity. The mode add-drop technology is an important part of the MDM system and a key element for realizing flexible networking. In this paper, a mode add-drop technology based on few-mode fiber Bragg grating (FM-FBG) is reported for the first time. The technology utilizes the reflection characteristics of Bragg grating to realize the add-drop function in the MDM system. The grating is written in parallel according to the optical field distribution characteristics of different modes. By changing the writing grating spacing Δa to match the optical field energy distribution of the few-mode fiber, the few-mode fiber grating with high self-coupling reflectivity for the high-order mode is fabricated, and the performance of the add-drop technology is improved. The mode add-drop technology is verified in a 3 x 3 MDM system, which uses quadrature phase shift keying (QPSK) modulation and coherence detection. The experimental results show that the excellent transmission, add, and drop of 3 x 8 Gbit/s QPSK signals in 8 km few-mode fibers are achieved. The realization of this mode add-drop technology only requires Bragg gratings, few-mode fiber circulators, and optical couplers. It has the advantages of high performance, simple structure, low cost, and easy implementation, and it can be widely used in the MDM system.
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Low-complexity decoding algorithms and ultra-high-order modulation formats are necessary to meet data rate requirements in excess of 1 Tbps. The information bottleneck algorithm has been effectively applied to the LDPC decoding algorithm in recent years, and its performance is comparable to that of the double-precision information propagation technique. However, the application of information bottleneck decoding algorithms in ultra-high order modulation forms has received little attention. Furthermore, the number of table lookups required for a single decoding loop is square to the node degree, which is undesirable for optical communications. We present a low-complexity LDPC decoding technique for ultra-high-order modulated signals in this study. First, the algorithm employs multivariate covariates to build an information bottleneck framework, which introduces the processing required for applying the information bottleneck algorithm to 1024-QAM signals and the requirement of combining higher-order modulation formats with LDPC codes. The technique makes use of a bidirectional recursive network and the symmetry of quantized information to reuse the same set of tables, considerably reducing the number of table lookup operations required in the decoding process. Constructing a coherent optical communication system with 1024-QAM signals proves that the proposed algorithm can operate effectively. The performance sacrifice of 0.2 â¼ 0.3 dB reduces the number of table lookup operations required for decoding from square to linear magnitude, which greatly reduces the decoding time required in optical communication.
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Five novel bis-tridentate Ir(III) complexes (Ir-1−Ir-5) incorporating versatile N^N^C ligands and a N^C^N ligand (1,3-di(2-pyridyl)-4,6-dimethylbenzene) were synthesized. With the combination of experimental and theoretical methods, their steady and transient state characteristics were researched scientifically. The UV-visible absorption spectra show that the broadband charge transfer absorbance of those bis-tridentate Ir(III) complexes can reach 550 nm, all of these complexes reveal the long-lasting phosphorescent emission. Because the excited-state absorption is more powerful than the ground-state absorption, a sturdy reverse saturable absorption (RSA) process can ensue in the visible and near-infrared regions when the complexes are exposed to a 532 nm laser. Therefore, the optical power limiting (OPL) effect follows the trend: Ir-5 > Ir-4 ≈ Ir-3 > Ir-2 > Ir-1. Generally speaking, the expansion of π-conjugation and the introduction of electron donating/withdrawing groups on the N^N^C ligand could effectively elevate the OPL effect. Therefore, these octahedral bis-tridentate Ir(III) complexes might be exploited as potential OPL materials.
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In vivo optical imaging is an important application value in disease diagnosis. However, near-infrared nanoprobes with excellent luminescent properties are still scarce. Herein, two boron-dipyrromethene (BODIPY) molecules (BDP-A and BDP-B) were designed and synthesized. The BODIPY emission was tuned to the near-infrared (NIR) region by regulating the electron-donating ability of the substituents on its core structure. In addition, the introduction of polyethylene glycol (PEG) chains on BODIPY enabled the formation of self-assembled nanoparticles (NPs) to form optical nanoprobes. The self-assembled BODIPY NPs present several advantages, including NIR emission, large Stokes shifts, and high fluorescence quantum efficiency, which can increase water dispersibility and signal-to-noise ratio to decrease the interference by the biological background fluorescence. The in vitro studies revealed that these NPs can enter tumor cells and illuminate the cytoplasm through fluorescence imaging. Then, BDP-B NPs were selected for use in vivo imaging due to their unique NIR emission. BDP-B was enriched in the tumor and effectively illuminated it via an enhanced penetrability and retention effect (EPR) after being injected into the tail vein of mice. The organic nanoparticles were metabolized through the liver and kidney. Thus, the BODIPY-based nanomicelles with NIR fluorescence emission provide an effective research basis for the development of optical nanoprobes in vivo.
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Boro , Nanopartículas , Ratones , Animales , Fluorescencia , Nanopartículas/químicaRESUMEN
Three A-π-A or D-π-D perylene diimide (PDI) derivatives with varied groups on π-conjugate were synthesized and characterized. The photophysical properties of these compounds were systematically studied by spectral experiments and density functional theory calculations. All compounds displayed intense absorption bands at 300-800 nm wavelengths. However, diverse groups on the π-conjugate influenced the UV-vis absorption. Electron-withdrawing groups on PDI-2 caused a slight red shift at the 350-400 nm wavelength and a blue shift after 400 nm wavelength. At the same time, the electron-donating substituents on PDI-3 caused an obvious red shift of this band. These PDI derivatives exhibited emission in solution at room temperature (λem = 500-850 nm). The quantum yield of PDI-3 decreased, while the electron-donating substituents were introduced to the π-conjugated motifs. However, the quantum yield of PDI-2 increased when electron-withdrawing substituents were introduced to the π-conjugated motifs. In addition, PDI-1 and PDI-2 exhibited broad triplet transient absorption in the visible region. These photophysical properties could help us to understand the relationship between structure and photophysical properties of perylene diimide derivatives and exploit more original perylene diimide-based optical functional materials.
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Perileno , Fenómenos Químicos , Electrones , LuminiscenciaRESUMEN
BACKGROUND: Uterus corpus endometrial cancer (UCEC) is the main malignant tumor in gynecology, with a high degree of heterogeneity, especially in terms of prognosis and immunotherapy efficacy. DNA methylation is one of the most important epigenetic modifications. Studying DNA methylation can help predict the prognosis of cancer patients and provide help for clinical treatment. Our research aims to discover whether abnormal DNA methylation can predict the prognosis of UCEC and reflect the patient's tumor immune microenvironment. PATIENTS AND METHODS: The clinical data, DNA methylation data, gene expression data and somatic mutation data of UCEC patients were all downloaded from the TCGA database. The MethylMix algorithm was used to integrate DNA methylation data and mRNA expression data. Univariate Cox regression analysis, Multivariate Cox regression analysis, and Lasso Cox regression analysis were used to determine prognostic DNA methylation-driven genes and to construct an independent prognostic index (MDS). ROC curve analysis and Kaplan-Meier survival curve analysis were used to evaluate the predictive ability of MDS. GSEA analysis was used to explore possible mechanisms that contribute to the heterogeneity of the prognosis of UCEC patients. RESULTS: 3 differential methylation-driven genes (DMDGs) (PARVG, SYNE4 and CDO1) were considered as predictors of poor prognosis in UCEC. An independent prognostic index was finally established based on 3 DMDGs. From the results of ROC curve analysis and survival curve analysis, MDS showed excellent prognostic ability in TCGA-UCEC. A new nomogram based on MDS and other prognostic clinical indicators has also been successfully established. The C-index of the nomogram for OS prediction was 0.764 (95% CI = 0.702-0.826). GSEA analysis suggests that there were differences in immune-related pathways among patients with different prognosis. The abundance of M2 macrophages and M0 macrophages were significantly enhanced in the high-risk group while T cells CD8, Eosinophils and Neutrophils were markedly elevated in the low-risk group. Meanwhile, patients in the low-risk group had higher levels of immunosuppressant expression, higher tumor mutational burden and immunophenoscore (IPS) scores. Joint survival analysis revealed that 7 methylation-driven genes could be independent prognostic factors for overall survival for UCEC. CONCLUSION: We have successfully established a risk model based on 3 DMDGs, which could accurately predict the prognosis of patients with UCEC and reflect the tumor immune microenvironment.
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A family of novel bis-tridentate Ir(III) complexes (Ir1-Ir5) incorporating both functional Nâ§Câ§N-type ligands (L1-L5) and Nâ§Nâ§C-type ligand (L0) were synthesized attentively and characterized scientifically. The crystalline structures of Ir1, Ir3 and Ir4 were resoundingly confirmed by XRD. With the aid of experimental and theoretical methods, their photophysical properties at transient and steady states were scientifically investigated. The broadband charge-transfer absorption for these aforementioned Ir(III) complexes is up to 600 nm as shown in the UV-visible absorption spectrum. The emission lifetimes of their excited states are good. Between the visible and near-infrared regions, Ir1-Ir5 possessed powerful excited-state absorption. Hence, a remarkably robust reverse saturable absorption (RSA) process can occur once the complexes are irradiated by a 532 nm laser. The RSA effect follows the descending order: Ir3 > Ir5 > Ir4 ≈ Ir1 > Ir2. To sum up, modifying electron-donating units (-OCH3) and large π-conjugated units to the pyridyl Nâ§Câ§N-type ligands is a systematic way to markedly raise the RSA effect. Therefore, these octahedral bis-tridentate Ir(III) complexes are potentially state-of-the-art optical limiting (OPL) materials.
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In this work, we depict the synthesis and characterization of a series of meso-substituted boron-dipyrromethene (BODIPY) compounds. Their optical and electrochemical properties were investigated systematically. All these compounds exhibited intense absorption bands in the ultraviolet (UV) and visible regions, which arise from the π-π* transitions based on their BODIPY core segments. By comparing electron-withdrawing substituents and electron-donating substituents, we found that these compounds exhibited some similar photophysical properties but exhibited different fluorescence in the solid state. All compounds were highly emissive in dichloromethane at room temperature (λem = 512-523 nm, ΦPL > 0.9). When these compounds were applied in blue-driven light-emitting diodes (LEDs) as light-emitting materials, the devices showed luminescence efficiency ranging from 1.09 to 34.13 lm/W. Their luminescence and electrochemical properties could be used for understanding the structure-property relationship of BODIPY compounds and developing functional fluorescent materials.
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Boro , Porfobilinógeno , Compuestos de Boro , Luminiscencia , Porfobilinógeno/análogos & derivadosRESUMEN
Three new bis-photochromic molecules containing two 4,5-diarylimidazole units were synthesized and characterized. We investigated their photophysical properties and pH response characteristics in acetonitrile solutions and polymethylmethacrylate (PMMA) membranes. All compounds displayed significant pH responses for the imidazole ring in the molecular structure, which could be potentially used as pH probes. Under ultraviolet light, these compounds show photochromism and 'turn-off' fluorescence properties either in solution or in PMMA film. The mechanism of this phenomenon may be due to photoisomerization, that is the conversion of the 4,5-diarylimidazole units open-ring form to the closed-ring form. Moreover, such systems as logic gates, high density (3D) data storage systems and optical equivalents of field-effect transistors are considered necessary for optical computing.
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Etilenos , Rayos Ultravioleta , Fluorescencia , Estructura MolecularRESUMEN
The coronavirus disease 2019 (COVID-19) has grown up to be a pandemic within a short span of time. To investigate transmission dynamics and then determine control methodology, we took epidemic in Wuhan as a study case. Unfortunately, to our best knowledge, the existing models are based on the common assumption that the total population follows a homogeneous spatial distribution, which is not the case for the prevalence occurred both in the community and in hospital due to the difference in the contact rate. To solve this problem, we propose a novel epidemic model called SEIR-HC, which is a model with two different social circles (i.e., individuals in hospital and community). Using the model alongside the exclusive optimization algorithm, the spread process of COVID-19 epidemic in Wuhan city is reproduced and then the propagation characteristics and unknown data are estimated. The basic reproduction number of COVID-19 is estimated to be 7.9, which is far higher than that of the severe acute respiratory syndrome (SARS). Furthermore, the control measures implemented in Wuhan are assessed and the control methodology of COVID-19 is discussed to provide guidance for limiting the epidemic spread.
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STUDY DESIGN: Cross-sectional descriptive study. OBJECTIVES: To compare the diffusion tensor imaging (DTI) changes of the sacral cord in people with complete cervical spinal cord injury (SCI) and neurogenic bladder versus people without SCI, and to explore the relationship between sacral cord DTI changes and bladder contractility. SETTING: First Affiliated Hospital of Soochow University, Jiangsu Province, China. METHODS: Forty participants were included: 25 participants with complete cervical SCI and 15 without SCI. Fractional anisotropy (FA) and apparent diffusion coefficient (ADC) values were calculated by DTI for ventral horn and intermediate column of sacral cord at S2-S4 level. All participants underwent urodynamic examination. The urodynamic parameters (voiding efficiency (VE), and bladder contractility index (BCI)) and DTI parameters were compared between people with and without SCI. The correlations between DTI values (FA and ADC) and urodynamic parameters were analyzed. RESULTS: The FA values were significantly lower and the ADC values were significantly higher in the intermediate column and ventral horn at S2-S4 level of the participants with SCI compared with their able-bodied counterparts (p < 0.05). VE and BCI were significantly different between the two groups (p < 0.05). The FA values of intermediate column positively correlated with BCI (r = 0.749, p < 0.05) and the ADC values negatively correlated with BCI (r = -0.471, p < 0.05) in participants with SCI. The DTI values of sacral cord were not correlated with each urodynamic parameter in participants without SCI (p > 0.05). CONCLUSIONS: Complete cervical SCI might lead to microstructural changes of the sacral cord, which might further affect bladder contraction.
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Imagen de Difusión Tensora , Traumatismos de la Médula Espinal , Anisotropía , Estudios Transversales , Humanos , Cuadriplejía , Médula Espinal , Traumatismos de la Médula Espinal/complicaciones , Traumatismos de la Médula Espinal/diagnóstico por imagen , Vejiga Urinaria/diagnóstico por imagenRESUMEN
Like other tumors, lung cancer must induce angiogenesis as it grows. Hypoxia-inducible factor 1α (HIF-1α) is the inducible subunit of the HIF-1 transcription factor that regulates genes involved in the response to hypoxia, some of which contributes to angiogenesis. Vascular endothelial growth factor (VEGF) is one of the genes upregulated by HIF-1 and is the primary cytokine in relation to angiogenesis. In this study we tested whether aberrant activation of hypoxia inducible factor-1α/vascular endothelial growth factor (HIF-1α/VEGF) pathway correlates with response to radiotherapy and examined the response of lung cancer cells to hypoxia in vitro. We determined increased expressions of HIF-1α and VEGF-A in 76 cancerous tissues of responders (complete remission and partial remission). HIF-1α and VEGF-A were shown to be upregulated in lung cancer cells in response to hypoxia. The treatment with anti-HIF-1α siRNA prior to hypoxia exposure was shown to decrease HIF-1α and VEGF-A expressions and reduce hypoxia-induced angiogenesis, suggesting that HIF-1α expression resulted in increased VEGF-A expression and activation of HIF-1α/VEGF pathway was responsible for hypoxia-induced angiogenesis. In conclusion, we identified the relationship between HIF-1α/VEGF pathway and response to radiotherapy and its role in angiogenesis in lung cancer in vitro. HIF-1α/VEGF pathway as a target for antiangiogenic treatment strategies for this tumor requires further investigation.
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Subunidad alfa del Factor 1 Inducible por Hipoxia/genética , Subunidad alfa del Factor 1 Inducible por Hipoxia/metabolismo , Neoplasias Pulmonares/radioterapia , Regulación hacia Arriba/efectos de la radiación , Factor A de Crecimiento Endotelial Vascular/genética , Células A549 , Adulto , Anciano , Animales , Hipoxia de la Célula/efectos de los fármacos , Línea Celular Tumoral , Femenino , Regulación Neoplásica de la Expresión Génica/efectos de la radiación , Humanos , Subunidad alfa del Factor 1 Inducible por Hipoxia/antagonistas & inhibidores , Neoplasias Pulmonares/genética , Neoplasias Pulmonares/metabolismo , Masculino , Ratones , Persona de Mediana Edad , ARN Interferente Pequeño/farmacología , Transducción de Señal/efectos de los fármacos , Transducción de Señal/efectos de la radiación , Resultado del Tratamiento , Factor A de Crecimiento Endotelial Vascular/metabolismo , Ensayos Antitumor por Modelo de XenoinjertoRESUMEN
BACKGROUND: Obesity is found to increase the risk of most cancer types, but reduce lung cancer risk in many studies. However, the association between obesity and lung cancer is still controversial, mainly owing to the confounding effect of smoking. METHODS: Eligible studies were identified from electric databases to July 1, 2017. Relevant data were extracted and pooled using random-effects models; dose-response and subgroup analyses were also performed. RESULTS: Twenty-nine studies with more than 10,000 lung cancer cases in15 million never smokers were included. Compared with normal weight, the summary relative risk (RR) was 0.77(95% confidence interval [CI]: 0.68-0.88, P < 0.01) for excess body weight (body mass index [BMI] ≥ 25 kg/m2). An inverse linear dose-response relationship was observed between BMI and lung cancer risk in never smokers, with an RR of 0.89(95% CI: 0.84-0.95, P < 0.01) per 5 kg/m2 increment in BMI. The results remained stable in most subgroup analyses. However, when stratified by sex, a significant inverse association existed in women but not in men. Similar results were found in analyses for other categories of BMI. CONCLUSION: Our results indicate that higher BMI is associated with lower lung cancer risk in never smokers.
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Neoplasias Pulmonares/epidemiología , Obesidad/complicaciones , Índice de Masa Corporal , Humanos , Factores de Riesgo , FumadoresRESUMEN
Cardiac resynchronization therapy (CRT) improves heart function and prognosis in third-degree atrioventricular block (AVB) patients with heart failure (HF). However, it is still unclear how to screen for appropriate patients before implantation. This study aimed to evaluate the value of using QRS duration to predict CRT efficacy.This study enrolled a total of 72 third-degree AVB patients with HF who received CRT implantation. The patients were divided into Groups A (QRS duration < 120 ms, 33 cases), B (120 ms ≤ QRS duration < 150 ms, 22 cases), and C (QRS duration ≥ 150 ms, 17 cases) according to their baseline QRS duration. The effects of different QRS durations on CRT efficacy were analyzed.The CRT response rate were 30.3%, 50.0%, and 76.5% in Groups A, B, and C, respectively (P = 0.008). The patients in the 3 groups showed significant changes in left ventricular (LV) end-diastolic volume, LV end-systolic volume, and LV ejection fraction over the baseline values at 12 months after the implantation (P < 0.05), with the greatest change observed in Group C. Survival analysis indicated statistically significant differences among Groups A, B, and C (P = 0.024). Multivariate logistic regression analysis suggested that QRS duration was an independent prognostic factor for CRT efficacy. Baseline QRS duration was associated with improved myocardial remodeling and reductions in the incidence rates of primary endpoint events.QRS ≥ 150 ms is an effective predictor of postoperative outcome in patients with third-degree AVB and HF treated with CRT.
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Bloqueo Atrioventricular/terapia , Terapia de Resincronización Cardíaca , Insuficiencia Cardíaca/etiología , Anciano , Anciano de 80 o más Años , Bloqueo Atrioventricular/complicaciones , Bloqueo Atrioventricular/mortalidad , Bloqueo Atrioventricular/fisiopatología , Femenino , Estudios de Seguimiento , Insuficiencia Cardíaca/mortalidad , Humanos , Estimación de Kaplan-Meier , Modelos Logísticos , Masculino , Persona de Mediana Edad , Pronóstico , Resultado del TratamientoRESUMEN
Polysaccharides from Ascophyllum nodosum (AnPS) were extracted and purified via an optimized protocol. The optimal extraction conditions were as follows: extraction time of 4.3 h, extraction temperature of 84 °C and ratio (v/w, mL/g) of extraction solvent (water) to raw material of 27. The resulting yield was 9.15 ± 0.23% of crude AnPS. Two fractions, named AnP1-1 and AnP2-1 with molecular weights of 165.92 KDa and 370.68 KDa, were separated from the crude AnPS by chromatography in DEAE Sepharose Fast Flow and Sephacryl S-300, respectively. AnP1-1 was composed of mannose, ribose, glucuronic acid, glucose and fucose, and AnP2-1 was composed of mannose, glucuronic acid, galactose and fucose. AnPS, AnP1-1 and AnP2-1 exhibited high scavenging activities against ABTS radical and superoxide radical, and showed protective effect on H2O2-induced oxidative injury in RAW264.7 cells. Furthermore, the immunostimulatory activities of AnP1-1 and AnP2-1 were evaluated by Caco-2 cells, the results showed both AnP1-1 and AnP2-1 could significantly promote the production of immune reactive molecules such as interleukin (IL)-8, IL-1ß, interferon (IFN)-γ, and tumor necrosis factor (TNF)-α. Therefore, the results suggest that AnPS and its two fractions may be explored as a potential functional food supplement.
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Adyuvantes Inmunológicos/aislamiento & purificación , Antioxidantes/aislamiento & purificación , Ascophyllum/química , Extracción Líquido-Líquido/métodos , Polisacáridos/aislamiento & purificación , Adyuvantes Inmunológicos/química , Adyuvantes Inmunológicos/farmacología , Animales , Antioxidantes/química , Antioxidantes/farmacología , Células CACO-2 , Supervivencia Celular/efectos de los fármacos , Cromatografía DEAE-Celulosa , Fucosa/química , Fucosa/aislamiento & purificación , Galactosa/química , Galactosa/aislamiento & purificación , Ácido Glucurónico/química , Ácido Glucurónico/aislamiento & purificación , Humanos , Peróxido de Hidrógeno/antagonistas & inhibidores , Peróxido de Hidrógeno/farmacología , Interferón gamma/biosíntesis , Interferón gamma/inmunología , Interleucina-1beta/biosíntesis , Interleucina-1beta/inmunología , Interleucina-8/biosíntesis , Interleucina-8/inmunología , Manosa/química , Manosa/aislamiento & purificación , Ratones , Polisacáridos/química , Polisacáridos/farmacología , Células RAW 264.7 , Solventes/química , Sulfatos/química , Factor de Necrosis Tumoral alfa/biosíntesis , Factor de Necrosis Tumoral alfa/inmunología , Agua/químicaRESUMEN
An attractive and novel methodology involving Pd/Cu-catalyzed tandem head-to-tail dimerization/cycloisomerization of terminal ynamides for the synthesis of 3,5-disubstituted oxazolones was developed. Under Pd(PPh3)2Cl2/CuI cooperative catalyzed reaction conditions, it provided efficient access to 5-vinyloxazolones with exceptional functional group tolerance and good chemoselectivity. The control experiments demonstrated that Pd(PPh3)2Cl2 serves a key role in the dimerization of terminal ynamides and shows low catalytic activity in the intramolecular cyclization. Moreover, the hetero-Diels-Alder reaction of product 5-vinyloxazolones was also described, which provided polycyclic oxazolones in good yield.
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A highly regio- and stereoselective trans-iodofluorination reaction of ynamides with NIS and Et3N·3HF has been achieved, affording (E)-α-fluoro-ß-iodoenamides in moderate to good yields. The reaction proceeds under mild reaction conditions and exhibits good functional group compatibility.
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Amidas/química , Amidas/síntesis química , Halogenación , Yodo/química , Catálisis , Técnicas de Química Sintética , EstereoisomerismoRESUMEN
A novel method for metal-free oxothiolation of ynamides to construct oxazolidine-2,4-diones bearing sulfur-substituted quaternary carbon atoms has been developed. It represents a rare C-O bond cleavage of ynamides, as well as a facile and tandem approach for the formation of C-O, C-S, and C-Cl bonds. This redox-neutral protocol can be applied to the synthesis of multisubstituted oxazolidine-2,4-diones with good chemoselectivity and good yields of isolated products under mild conditions.
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With Et3N·3HF as the fluorination reagent, (IPr)CuF-catalyzed α-site regiocontrolled trans-hydrofluorination of ynamides has been achieved, affording (Z)-α-fluoroenamides in moderate to excellent yields. It was interesting to note that the regioselectivity of the reaction is reversed to that observed in the (Ph3P)3CuF-catalyzed hydrofluorination of ynamides. Additionally, a variety of different ynamides including oxazolidinonyl-, imidazolyl-, and N-sulfonyl ynamides were suitable for the reaction system and the subsequent oxidation of the fluorinated products enables a convenient synthesis to α-fluoroimides.