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Cross-coupling reactions are among the most important transformations in modern organic synthesis1-3. Although the range of reported (het)aryl halides and nucleophile coupling partners is very large considering various protocols, the reaction conditions vary considerably between compound classes, necessitating renewed case-by-case optimization of the reaction conditions4. Here we introduce adaptive dynamic homogeneous catalysis (AD-HoC) with nickel under visible-light-driven redox reaction conditions for general C(sp2)-(hetero)atom coupling reactions. The self-adjustive nature of the catalytic system allowed the simple classification of dozens of various classes of nucleophiles in cross-coupling reactions. This is synthetically demonstrated in nine different bond-forming reactions (in this case, C(sp2)-S, Se, N, P, B, O, C(sp3, sp2, sp), Si, Cl) with hundreds of synthetic examples under predictable reaction conditions. The catalytic reaction centre(s) and conditions differ from one another by the added nucleophile, or if required, a commercially available inexpensive amine base.
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BACKGROUND AND AIMS: HBV and HIV coinfection is a common occurrence globally, with significant morbidity and mortality. Both viruses lead to immune dysregulation including changes in natural killer (NK) cells, a key component of antiviral defense and a promising target for HBV cure strategies. Here we used high-throughput single-cell analysis to explore the immune cell landscape in people with HBV mono-infection and HIV/HBV coinfection, on antiviral therapy, with emphasis on identifying the distinctive characteristics of NK cell subsets that can be therapeutically harnessed. APPROACH AND RESULTS: Our data show striking differences in the transcriptional programs of NK cells. HIV/HBV coinfection was characterized by an over-representation of adaptive, KLRC2 -expressing NK cells, including a higher abundance of a chemokine-enriched ( CCL3/CCL4 ) adaptive cluster. The NK cell remodeling in HIV/HBV coinfection was reflected in enriched activation pathways, including CD3ζ phosphorylation and ZAP-70 translocation that can mediate stronger antibody-dependent cellular cytotoxicity responses and a bias toward chemokine/cytokine signaling. By contrast, HBV mono-infection imposed a stronger cytotoxic profile on NK cells and a more prominent signature of "exhaustion" with higher circulating levels of HBsAg. Phenotypic alterations in the NK cell pool in coinfection were consistent with increased "adaptiveness" and better capacity for antibody-dependent cellular cytotoxicity compared to HBV mono-infection. Overall, an adaptive NK cell signature correlated inversely with circulating levels of HBsAg and HBV-RNA in our cohort. CONCLUSIONS: This study provides new insights into the differential signature and functional profile of NK cells in HBV and HIV/HBV coinfection, highlighting pathways that can be manipulated to tailor NK cell-focused approaches to advance HBV cure strategies in different patient groups.
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Citotoxicidad Celular Dependiente de Anticuerpos , Coinfección , Infecciones por VIH , Células Asesinas Naturales , Humanos , Infecciones por VIH/inmunología , Infecciones por VIH/complicaciones , Células Asesinas Naturales/inmunología , Coinfección/inmunología , Masculino , Femenino , Adulto , Hepatitis B/inmunología , Hepatitis B/complicaciones , Persona de Mediana Edad , Hepatitis B Crónica/inmunología , Hepatitis B Crónica/complicaciones , Hepatitis B Crónica/virologíaRESUMEN
Chronic hepatitis B infection (CHB) affects 300 million people worldwide and is being targeted by the United Nations 2030 Sustainable Development Goals (SDGs) and the World Health Organisation (WHO), working towards elimination of hepatitis B virus (HBV) as a public health threat. In this piece, we explore the evidence and potential impact of peer support to enhance and promote interventions for people living with CHB. Peer support workers (PSWs) are those with lived experience of an infection, condition or situation who work to provide support for others, aiming to improve education, prevention, treatment and other clinical interventions and to reduce the physical, psychological and social impacts of disease. Peer support has been shown to be a valuable tool for improving health outcomes for people living with human immunodeficiency virus (HIV) and hepatitis C virus (HCV), but to date has not been widely available for communities affected by HBV. HBV disproportionately affects vulnerable and marginalised populations, who could benefit from PSWs to help them navigate complicated systems and provide advocacy, tackle stigma, improve education and representation, and optimise access to treatment and continuity of care. The scale up of peer support must provide structured and supportive career pathways for PSWs, account for social and cultural needs of different communities, adapt to differing healthcare systems and provide flexibility in approaches to care. Investment in peer support for people living with CHB could increase diagnosis, improve retention in care, and support design and roll out of interventions that can contribute to global elimination goals.
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Hepatitis B Crónica , Grupo Paritario , Apoyo Social , Humanos , Hepatitis B Crónica/terapia , Hepatitis B Crónica/psicologíaRESUMEN
Diagnosing and treating chronic hepatitis B virus (HBV) infection are key interventions to support progress towards elimination of viral hepatitis by 2030. Although nucleos/tide analogue (NA) therapy is typically highly effective, challenges remain for viral load (VL) suppression, including medication access, incomplete adherence and drug resistance. We present a case of a long-term HBV and HIV coinfected adult prescribed with sequential NA therapy regimens, with episodes of breakthrough viraemia. Multiple factors contribute to virological breakthrough, including exposure to old NA agents, initial high HBV VL, therapy interruptions, intercurrent illnesses and potential contribution from resistance mutations. The case underscores the importance of individualised treatment approaches and adherence support in achieving HBV suppression. Furthermore, it emphasises the need for improved clinical pathways addressing education, support and access to care, particularly for marginalised populations. Comprehensive data collection inclusive of under-represented individuals is crucial for maintaining retention in the care cascade and informing effective interventions.
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Antivirales , Infecciones por VIH , Virus de la Hepatitis B , Hepatitis B Crónica , Carga Viral , Viremia , Adulto , Humanos , Persona de Mediana Edad , Antivirales/uso terapéutico , Coinfección/tratamiento farmacológico , Farmacorresistencia Viral , Guanina/análogos & derivados , Guanina/uso terapéutico , Virus de la Hepatitis B/efectos de los fármacos , Virus de la Hepatitis B/genética , Hepatitis B Crónica/tratamiento farmacológico , Infecciones por VIH/tratamiento farmacológico , Factores de Riesgo , Viremia/tratamiento farmacológicoRESUMEN
The developing world has been facing a significant health issue due to cholera as an endemic communicable disease. Lusaka was Zambia's worst affected province, with 5414 reported cases of cholera during the outbreak from late October 2017 to May 12, 2018. To explore the epidemiological characteristics associated with the outbreak, we fitted weekly reported cholera cases with a compartmental disease model that incorporates two transmission routes, namely environment-to-human and human-to-human. Estimates of the basic reproduction number show that both transmission modes contributed almost equally during the first wave. In contrast, the environment-to-human transmission appears to be mostly dominating factor for the second wave. Our study finds that a massive abundance of environmental vibrio's with a huge reduction in water sanitation efficacy triggered the secondary wave. To estimate the expected time to extinction (ETE) of cholera, we formulate the stochastic version of our model and find that cholera can last up to 6.5-7 years in Lusaka if any further outbreak occurs at a later time. Results indicate that a considerable amount of attention is to be paid to sanitation and vaccination programs in order to reduce the severity of the disease and to eradicate cholera from the community in Lusaka.
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Cólera , Humanos , Cólera/epidemiología , Cólera/prevención & control , Zambia/epidemiología , Conceptos Matemáticos , Modelos Biológicos , Brotes de EnfermedadesRESUMEN
BACKGROUND: Modeling of the London hepatitis C virus (HCV) epidemic in men who have sex with men (MSM) and are living with human immunodeficiency virus (HIV) suggested that early access to direct-acting antiviral (DAA) treatment may reduce incidence. With high rates of linkage to care, microelimination of HCV within MSM living with HIV may be realistic ahead of 2030 World Health Organization targets. We examined trends in HCV incidence in the pre- and post-DAA eras for MSM living with HIV in London and Brighton, United Kingdom. METHODS: A retrospective cohort study was conducted at 5 HIV clinics in London and Brighton between 2013 and 2018. Each site reported all acute HCV episodes during the study period. Treatment timing data were collected. Incidence rates and reinfection proportion were calculated. RESULTS: A total of.378 acute HCV infections were identified, comprising 292 first infections and 86 reinfections. Incidence rates of acute HCV in MSM living with HIV peaked at 14.57/1000 person-years of follow-up (PYFU; 95% confidence interval [CI], 10.95-18.20) in 2015. Rates fell to 4.63/1000 PYFU (95% CI, 2.60 to 6.67) by 2018. Time from diagnosis to starting treatment declined from 29.8 (2013) to 3.7 months (2018). CONCLUSIONS: We observed a 78% reduction in the incidence of first HCV episode and a 68% reduction in overall HCV incidence since the epidemic peak in 2015, which coincides with wider access to DAAs in England. Further interventions to reduce transmission, including earlier access to treatment and for reinfection, are likely needed for microelimination to be achieved in this population.
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Infecciones por VIH , Hepatitis C Crónica , Hepatitis C , Minorías Sexuales y de Género , Antivirales/uso terapéutico , Inglaterra , VIH , Infecciones por VIH/complicaciones , Infecciones por VIH/tratamiento farmacológico , Infecciones por VIH/epidemiología , Hepacivirus , Hepatitis C/tratamiento farmacológico , Hepatitis C/epidemiología , Hepatitis C/prevención & control , Hepatitis C Crónica/tratamiento farmacológico , Homosexualidad Masculina , Humanos , Incidencia , Londres/epidemiología , Masculino , Estudios Retrospectivos , Reino Unido/epidemiologíaRESUMEN
The ongoing COVID-19 pandemic has affected most of the countries on Earth. It has become a pandemic outbreak with more than 50 million confirmed infections and above 1 million deaths worldwide. In this study, we consider a mathematical model on COVID-19 transmission with the prosocial awareness effect. The proposed model can have four equilibrium states based on different parametric conditions. The local and global stability conditions for awareness-free, disease-free equilibrium are studied. Using Lyapunov function theory and LaSalle invariance principle, the disease-free equilibrium is shown globally asymptotically stable under some parametric constraints. The existence of unique awareness-free, endemic equilibrium and unique endemic equilibrium is presented. We calibrate our proposed model parameters to fit daily cases and deaths from Colombia and India. Sensitivity analysis indicates that the transmission rate and the learning factor related to awareness of susceptibles are very crucial for reduction in disease-related deaths. Finally, we assess the impact of prosocial awareness during the outbreak and compare this strategy with popular control measures. Results indicate that prosocial awareness has competitive potential to flatten the COVID-19 prevalence curve.
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Middle East Respiratory Syndrome Coronavirus (MERS-CoV) can cause mild to severe acute respiratory illness with a high mortality rate. As of January 2020, more than 2500 cases of MERS-CoV resulting in around 860 deaths were reported globally. In the absence of neither effective treatment nor a ready-to-use vaccine, control measures can be derived from mathematical models of disease epidemiology. In this manuscript, we propose and analyze a compartmental model of zoonotic MERS-CoV transmission with two co-circulating strains. The human population is considered with eight compartments while the zoonotic camel population consist of two compartments. The expression of basic reproduction numbers are obtained for both single strain and two strain version of the proposed model. We show that the disease-free equilibrium of the system with single stain is globally asymptotically stable under some parametric conditions. We also demonstrate that both models undergo backward bifurcation phenomenon, which in turn indicates that only keeping R 0 below unity may not ensure eradication. To the best of the authors knowledge, backward bifurcation was not shown in a MERS-CoV transmission model previously. Further, we perform normalized sensitivity analysis of important model parameters with respect to basic reproduction number of the proposed model. Furthermore, we perform optimal control analysis on different combination interventions with four components namely preventive measures such as use of masks, isolation of strain-1 infected people, strain-2 infected people and infected camels. Optimal control analysis suggests that combination of preventive measures and isolation of infected camels will eventually eradicate the disease from the community.
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An outbreak of respiratory disease caused by a novel coronavirus is ongoing from December 2019. As of December 14, 2020, it has caused an epidemic outbreak with more than 73 million confirmed infections and above 1.5 million reported deaths worldwide. During this period of an epidemic when human-to-human transmission is established and reported cases of coronavirus disease 2019 (COVID-19) are rising worldwide, investigation of control strategies and forecasting are necessary for health care planning. In this study, we propose and analyze a compartmental epidemic model of COVID-19 to predict and control the outbreak. The basic reproduction number and the control reproduction number are calculated analytically. A detailed stability analysis of the model is performed to observe the dynamics of the system. We calibrated the proposed model to fit daily data from the United Kingdom (UK) where the situation is still alarming. Our findings suggest that independent self-sustaining human-to-human spread ( R 0 > 1 , R c > 1 ) is already present. Short-term predictions show that the decreasing trend of new COVID-19 cases is well captured by the model. Further, we found that effective management of quarantined individuals is more effective than management of isolated individuals to reduce the disease burden. Thus, if limited resources are available, then investing on the quarantined individuals will be more fruitful in terms of reduction of cases.
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Herein, a visible-light photochemical approach for practical helicene functionalization at very mild reaction conditions is described. The photochemical reactions allow for the regiospecific and innate late-stage functionalization of helicenes and are easily executed either through the activation of C(sp2 )-Br bonds in helicenes using K2 CO3 as inorganic base or direct C(sp2 )-H helicene bond functionalization under oxidative photoredox reaction conditions. Overall, using these transformations six different functional groups are introduced to the helicene scaffold through C-C and four different C-heteroatom bond-forming reactions.
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Luz , Compuestos Policíclicos/química , Carbonatos/química , Catálisis , Oxidación-Reducción , Potasio/química , Teoría CuánticaRESUMEN
The coronavirus disease 2019 (COVID-19) has become a public health emergency of international concern affecting 201 countries and territories around the globe. As of April 4, 2020, it has caused a pandemic outbreak with more than 11,16,643 confirmed infections and more than 59,170 reported deaths worldwide. The main focus of this paper is two-fold: (a) generating short term (real-time) forecasts of the future COVID-19 cases for multiple countries; (b) risk assessment (in terms of case fatality rate) of the novel COVID-19 for some profoundly affected countries by finding various important demographic characteristics of the countries along with some disease characteristics. To solve the first problem, we presented a hybrid approach based on autoregressive integrated moving average model and Wavelet-based forecasting model that can generate short-term (ten days ahead) forecasts of the number of daily confirmed cases for Canada, France, India, South Korea, and the UK. The predictions of the future outbreak for different countries will be useful for the effective allocation of health care resources and will act as an early-warning system for government policymakers. In the second problem, we applied an optimal regression tree algorithm to find essential causal variables that significantly affect the case fatality rates for different countries. This data-driven analysis will necessarily provide deep insights into the study of early risk assessments for 50 immensely affected countries.
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Dengue control in India is a challenging task due to complex healthcare settings. In yesteryears, an amplification of dengue infections in India posed the need for introspection of existing dengue control policies. Prior understanding of the impacts of control interventions is necessary for their future implementation. In this paper, we propose and analyze a compartmental model of dengue to assess the impact of active case finding (ACF) on dengue disease transmission. Currently, primary prevention of dengue is possible only with vector control and personal protection from the bites of infected mosquitoes. Although a few experimental studies are performed to assess ACF in dengue disease, but this is the first attempt to represent and study the dynamics of disease using ACF as a control strategy. Local and global dynamics of the system are studied. We use sensitivity analysis to see the effects of controllable parameters of the model on the basic reproduction number and total number of infective population. We find that decrease in the biting rate of mosquitoes, and increase in the rate of hospitalization and/or notification, death rate of mosquitoes and ACF for asymptomatic and symptomatic individuals play crucial role for the reduction of disease prevalence. We calibrate our model to the yearly dengue cases in eight dengue endemic states of India. The results of our study show that ACF of symptomatic individuals will have significant effect on dengue case reduction but ACF of asymptomatic individuals cannot be ignored. Our findings indicate that the healthcare organizations must focus on ACF of symptomatic as well as asymptomatic individuals along with personal protection and mosquitoes control to achieve rapid reduction of dengue cases in India.
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Virus del Dengue , Dengue/prevención & control , Dengue/transmisión , Modelos Biológicos , Control de Mosquitos , Mosquitos Vectores/virología , Animales , Humanos , IndiaRESUMEN
The tricyclic aromatic ketone 9-anthrone and its derivatives are under basic conditions in equilibrium with their corresponding anionic forms. Unlike the neutral species, the 9-anthrolate anions can be excited by blue LED light and thus, are able to initiate a photoinduced electron transfer (PET) reaction. To demonstrate the synthetic applicability of the catalytic system, various (hetero)aryl chlorides were converted in C-C and C-Het bond-forming reactions affording the corresponding arylation products in moderate to excellent yields. The reactions proceed under very mild conditions without the need for a sacrificial electron donor. Besides 9-anthrone, other closely related derivatives were synthesised and investigated concerning their ability to catalyse demanding reductive transformations. Based on spectroscopic findings and radical trapping experiments a conceivable mechanism is proposed.
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In this work, we demonstrate that useful C-C bond-forming photoredox catalysis can be performed in air using easily prepared gel networks as reaction media to give similar results as are obtained under inert atmosphere conditions. These reactions are completely inhibited in homogeneous solution in air. However, the supramolecular fibrillar gel networks confine the reactants and block oxygen diffusion, allowing air-sensitive catalytic activity under ambient conditions. We investigate the mechanism of this remarkable protection, focusing on the boundary effect in the self-assembled supramolecular gels that enhances the rates of productive reactions over diffusion-controlled quenching of excited states. Our observations suggest the occurrence of triplet-sensitized chemical reactions in the gel networks within the compartmentalized solvent pools held between the nanofibers. The combination of enhanced viscosity and added interfaces in supramolecular gel media seems to be a key factor in facilitating the reactions under aerobic conditions.
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The recent Zika virus outbreak has been spreading rapidly all over the world, expanding its traditionally geographical affected regions, making it a global public health hazard and endangering millions of people. One unique property of the Zika virus compared to most vector-borne diseases is the fact that the virus is transmitted both by mosquitoes and by direct sexual contact. In the present manuscript, we formulate and analyze five mathematical compartmental models of Zika transmission. We model both transmission routes (i.e., vector-borne and sexual transmission). In order to make the model more realistic, heterogeneity in the sexual transmission is modeled in several ways. We fitted the five different models to data, inferred the parameters and selected the most appropriated model, which describes the Zika outbreak in Columbia. For all the models, we estimate the reproduction numbers, namely direct (sexual) transmission, vector transmission and the basic reproduction number [Formula: see text]. The analysis revealed that the sexual transmission contribution to [Formula: see text] is highest [15.36% (95% CI 12.83-17.4)] for the model which stratifies each gender to high-risk and low-risk individuals in their sexual behavior. For this model, the estimated [Formula: see text] is 1.89 (95% CI 1.21-2.13), the direct transmission reproduction number is 0.42 (95% CI 0.29-0.64), and the vector transmission reproduction number is 1.51 (95% CI 1.23-1.87). The sensitivity analysis demonstrated that the value of [Formula: see text] depends on three controllable parameters: the biting rate, the sexual transmission rate and the average ratio of mosquito to human.
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Modelos Biológicos , Infección por el Virus Zika/transmisión , Animales , Número Básico de Reproducción , Teorema de Bayes , Colombia/epidemiología , Simulación por Computador , Brotes de Enfermedades/estadística & datos numéricos , Femenino , Humanos , Recién Nacido , Funciones de Verosimilitud , Masculino , Cadenas de Markov , Conceptos Matemáticos , Método de Montecarlo , Mosquitos Vectores/virología , Embarazo , Conducta Sexual , Infección por el Virus Zika/epidemiologíaRESUMEN
Photoredox catalysis comprising homogeneous transition-metal-based systems, organic dyes, and semiconductors, has become a universal tool to catalyze a wide variety of chemical reactions with high selectivity and under mild conditions using visible light irradiation. This Minireview summarizes recent progress in photoredox catalysis mediated by heterogeneous carbon nitride materials such as mesoporous graphitic carbon nitride (mpg-CN), polymeric carbon nitride, and potassium poly(heptazine imides) (K-PHI). Because of the high thermal, chemical, and photostability of these materials, as well as favorable conduction and valence band positions, carbon nitrides expand the reaction range of photocatalysis to many novel reactions, such as photocatalytic activation of elemental sulfur to furnish a convenient chemical route to organosulfur compounds.
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UNLABELLED: In chronic hepatitis B (CHB), failure to control hepatitis B virus (HBV) is associated with T cell dysfunction. HBV transgenic mice mirror many features of the human disease, including T cell unresponsiveness, and thus represent an appropriate model in which to test novel therapeutic strategies. To date, the tolerant state of CD8(+) T cells in these animals could be altered only by strong immunogens or by immunization with HBV antigen-pulsed dendritic cells; however, the effectors induced were unable to suppress viral gene expression or replication. Because of the known stimulatory properties of alpha interferon (IFN-α) and interleukin-15 (IL-15), this study explored the therapeutic potential of liver-directed gene transfer of these cytokines in a murine model of CHB using adeno-associated virus (AAV) delivery. This combination not only resulted in a reduction in the viral load in the liver and the induction of an antibody response but also gave rise to functional and specific CD8(+) immunity. Furthermore, when splenic and intrahepatic lymphocytes from IFN-α- and IL-15-treated animals were transferred to new HBV carriers, partial antiviral immunity was achieved. In contrast to previous observations made using either cytokine alone, markedly attenuated PD-L1 induction in hepatic tissue was observed upon coadministration. An initial study with CHB patient samples also gave promising results. Hence, we demonstrated synergy between two stimulating cytokines, IL-15 and IFN-α, which, given together, constitute a potent approach to significantly enhance the CD8(+) T cell response in a state of immune hyporesponsiveness. Such an approach may be useful for treating chronic viral infections and neoplastic conditions. IMPORTANCE: With 350 million people affected worldwide and 600,000 annual deaths due to HBV-induced liver cirrhosis and/or hepatocellular carcinoma, chronic hepatitis B (CHB) is a major health problem. However, current treatment options are costly and not very effective and/or need to be administered for life. The unprecedented efficacy of the strategy described in our paper may offer an alternative and is relevant for a broad spectrum of readers because of its clear translational importance to other chronic viral infections in which a hyporesponsive antigen-specific T cell repertoire prevents clearance of the pathogen.
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Linfocitos T CD8-positivos/inmunología , Virus de la Hepatitis B/inmunología , Hepatitis B Crónica/inmunología , Hepatitis B Crónica/virología , Interferón-alfa/administración & dosificación , Interleucina-15/administración & dosificación , Adenoviridae/genética , Animales , Modelos Animales de Enfermedad , Portadores de Fármacos , Terapia Genética , Anticuerpos contra la Hepatitis B/sangre , Interferón-alfa/genética , Interleucina-15/genética , Hígado/virología , Ratones Transgénicos , Resultado del Tratamiento , Carga ViralRESUMEN
Introducing aryl- and heteroaryl moieties into molecular scaffolds are often key steps in the syntheses of natural products, drugs, or functional materials. A variety of cross-coupling methods have been well established, mainly using transition metal mediated reactions between prefunctionalized substrates and arenes or C-H arylations with functionalization in only one coupling partner. Although highly developed, one drawback of the established sp2-sp2 arylations is the required transition metal catalyst, often in combination with specific ligands and additives. Therefore, photoredox mediated arylation methods have been developed as alternative over the past decade. We begin our survey with visible light photo-Meerwein arylation reactions, which allow C-H arylation of heteroarenes, enones, alkenes, and alkynes with organic dyes, such as eosin Y, as the photocatalyst. A good number of examples from different groups illustrate the broad application of the reaction in synthetic transformations. While initially only photo-Meerwein arylation-elimination processes were reported, the reaction was later extended to photo-Meerwein arylation-addition reactions giving access to the photoinduced three component synthesis of amides and esters from alkenes, aryl diazonium salts, nitriles or formamides, respectively. Other substrates with redox-active leaving groups have been explored in photocatalyzed arylation reactions, such as diaryliodonium and triarylsulfonium salts, and arylsulfonyl chlorides. We discus some examples with their scope and limitations. The scope of arylation reagents for photoredox reactions was extended to aryl halides. The challenge here is the extremely negative reduction potential of aryl halides in the initial electron transfer step compared to, e.g., aryl diazonium or diaryliodonium salts. In order to reach reduction potentials over -2.0 V vs SCE two consecutive photoinduced electron transfer steps were used. The intermediary formed colored radical anion of the organic dye perylenediimide is excited by a second photon allowing the one electron reduction of acceptor substituted aryl chlorides. The radical anion of the aryl halide fragments under the loss of a halide ion and the aryl radical undergoes C-H arylation with biologically important pyrrole derivatives or adds to a double bond. Rhodamine 6G as an organic photocatalyst allows an even higher degree of control of the reaction. The dye is photoreduced in the presence of an amine donor under irradiation with green light (e.g., 530 nm), yielding its radical anion, which is a mild reducing reagent. The hypsochromic shift of the absorption of the rhodamine 6G radical anion toward blue region of the visible light spectrum allows its selective excitation using blue light (e.g., 455 nm). The excited radical anion is highly reducing and able to activate even bromoanisole for C-H arylation reactions, although only in moderate yield. Photoredox catalytic C-H arylation reactions are valuable alternatives to metal catalyzed reactions. They have an excellent functional group tolerance, could potentially avoid metal containing catalysts, and use visible light as a traceless reagent for the activation of arylating reagents.
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The direct transformation of ubiquitous, but chemically inert C-H bonds into diverse functional groups is an important strategy in organic synthesis that improves the atom economy and faclitates the preparation and modification of complex molecules. In contrast to the wide applications of aryl phosphonates, their synthesis via direct C-H bond phosphonylation is a less explored area. We report here a general, mild, and broadly applicable visible-light photoredox C-H bond phosphonylation method for electron-rich arenes and heteroarenes. The photoredox catalytic protocol utilizes electron-rich arenes and biologically important heteroarenes as substrates, [Ru(bpz)3 ][PF6 ]2 as photocatalyst, ammonium persulfate as oxidant, and trialkyl phosphites as the phosphorus source to provide a wide range of aryl phosphonates at ambient temperature under very mild reaction conditions.
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Influence of helicity on the excited-state as well as chiroptical properties of two sets of regiohelical coumarins that are differentiated by "inward" and "outward" disposition of the pyran-2-one ring has been investigated. A subtle difference in the helicities manifests in divergent excited-state properties and significant differences in the dipole moments. The latter permit heretofore unprecedented regiodifferentiation in the O-Hâ â â O hydrogen-bond assisted electron-transfer quenching by phenols. Furthermore, the enantiopure hexahelical coumarins exhibit strong Cotton effects and lend themselves to a very high differentiation in the specific rotations and anisotropic dissymmetry factors. The specific rotation observed for 6-in turns out being the highest of the values reported for all hexahelicenes reported so far.