Molecular phylogenetic analysis of the East Asian hemicultrine fishes (Teleostei: Cyprinidae: Xenocypridinae), with suggestions to their generic classification and redescription of the recently described species Hemiculter yungaoi Vasil'eva et al. 2022.

The hemicultrine fishes are a group of small-sized cyprinids, widely distributed but endemic to East Asian rivers and lakes. Till now, the taxonomic boundaries and relationships within this group remain poorly explored. In the present study, we study the phylogeny of this group, providing suggestions for classification of the hemicultrine group. Using two mitochondrial and three nuclear genes, and samples representing all genera, our results showed that the group consists of seven major lineages, of which four (Hemiculterella, Hainania, Pseudolaubuca, and Anabarilius) were monophyletic and three (Hemiculter, Toxabramis, and Pseudohemiculter) were not. Based on the phylogenetic tree, we redefined the genera. We revive the genus Siniichthys, which has three species, Siniichthys bleekeri, Siniichthys lucidus, and S. varpachovskii, that were previously treated as members of the genus Hemiculter but showed distant relationships to the genus Hemiculter in our phylogenetic tree. With the new results, a diagnostic key for clades of the hemicultrine group is provided. Furthermore, we provide more detailed information on diagnostic features of the recently described species Hemiculter yungaoi (Vasil'eva et al., 2022). This work will facilitate future systematic studies, pave the way for evolutionary studies, and provide valuable information for the urgent conservation of hemicultrine fishes.

Low-valent-tungsten catalysis enables hydroboration of esters and nitriles.

In the research presented herein, low-valent-tungsten-catalyzed hydroboration of esters and nitriles was investigated. Aromatic and aliphatic substrates were smoothly reduced to corresponding alcohol derivatives and N,N-diborylamines in the presence of W(CO)4(NCMe)2. Valuable derivatives were conveniently accessed by introducing a further functionalization process to crude hydroboration mixtures in one pot.

Effluent quality prediction of the sewage treatment based on a hybrid neural network model: Comparison and application.

The accurate prediction and assessment of effluent quality in wastewater treatment plants (WWTPs) are paramount for the efficacy of sewage treatment processes. Neural network models have exhibited promise in enhancing prediction accuracy by simulating and analyzing diverse influent parameters. In this study, a back propagation neural network hybrid model based on a tent chaotic map and sparrow search algorithm (Tent_BP_SSA) was developed to predict the effluent quality of sewage treatment processes. The prediction performance of the propose hybrid model was compared with traditional neural network models using five performance indicators (MAE, RMSE, SSE, MAPE and R2). Specifically, in comparison with the prior Tent_BP_SSA, Tent_BP_SSA2 demonstrated notable enhancements, with the R2 increasing from 0.9512 to 0.9672, while MAE, RMSE, SSE, and MAPE decreased by 9.62%, 18.84%, 24.80%, and 47.10%, respectively. These indicators collectively affirm that the utilization of higher-order input parameters ensures improved accuracy of the Tent_BP_SSA2 hybrid model in predicting effluent quality. Moreover, the Tent_BP_SSA2 model exhibited robust prediction ability (R2 of 0.9246) when applied to assess the effluent quality of an actual sewage treatment plant. The incorporation of integrated models comprising the sparrow search optimizing algorithm, tent chaotic mapping, and higher-order magnitude decomposition of input parameters has demonstrated the capacity to enhance the accuracy of effluent quality prediction. This study illuminates novel perspectives on the prediction of effluent quality and the assessment of effluent warnings in WWTPs.

Zwitterionic Aqua Palladacycles with Noncovalent Interactions for meta-Selective Suzuki Coupling of 3,4-Dichlorophenol and 3,4-Dichlorobenzyl Alcohol in Water.

The site-selective reaction of substrates with multiple reactive sites has been a focus of the current synthetic chemistry. The use of attractive noncovalent interactions between the catalyst and substrate is emerging as a versatile approach to address site-selectivity challenges. Herein, we designed and synthesized a series of palladacycles, to control meta-selective Suzuki coupling of 3,4-dichlorophenol and 3,4-dichlorobenzyl alcohol. Noncovalent interactions directed zwitterionic aqua palladacycles catalyzed meta-selective Suzuki couplings of 3,4-dichloroarenes bearing hydroxyl in water have been developed. Experiments and density functional theory (DFT) calculations demonstrated that the electrostatic interactions play a critical role in meta-selective coupling of 3,4-dichlorophenol, while meta-selective coupling of 3,4-dichlorobenzyl alcohol arises due to the hydrogen-bonding interactions.

Photocatalytic degradation of bisphenol A by temperature-sensitive magnetic hydrogel with enhanced service life.

Easy diffusion and low reusability limit the practicality of photocatalysts. In this study, a hollow sphere (HS) heterojunction was synthesized based on oxygen-doped carbon nitride (OCN) and layered double hydroxides (LDHs). A thermosensitive HS hydrogel (HS Gel) was prepared by mixing HS with N-isopropylacrylamide. Bisphenol A (BPA), being widely manufactured and used in commercial and domestical products and its high toxicity, was chosen as the target pollutant to demonstrate the photocatalytic ability and practicality of the HS Gel. HS Gel presented effective BPA degradation (95% degradation in 70 mins, 4.2 × 10-2 min-1 of kobs) at ambient temperature which is much better than kobs = 1.8 × 10-2 min-1 of OCN and kobs = 0.08 × 10-2 min-1 of LDH), and increased by two-fold the recycling service life (retention of >80% degradation efficiency after 13 usage cycles) compared to other carbon-based photocatalysts (retention of >80% degradation efficiency after 5-6 usage cycles). This is due to its multifunctional characteristics (magnetic property and thermal sensitivity). Under ambient temperature, the hydrophilic HS Gel swelled in the aqueous solution, which promoted the photocatalytic reaction between HS and BPA in the gel state. After the reaction, the HS Gel was subjected to shrinkage by high temperature heating to enhance the mechanical strength for recovery. The magnetic recovery was realized by the paramagnetic properties of layered double oxide to reduce environmental interference. Detailed studies of HS gel related to enhanced service life were conducted including structural changes, catalyst leaking and magnetic changing. A new kind of type Ӏ plus Z-scheme mechanism was also proposed based on the Kubelka-Munk equation, UV diffuse reflectance spectroscopy and Mott-Schotty technique.

Yolk-shell structured nanoreactor Au@Co3O4/CeO2@mSiO2 with superior peroxidase-like activity as nanozyme for ultra-sensitive colorimetric biosensing.

For yolk-shell structured nanoreactors, multiple active components can be precisely positioned on core and/or shell that can afford more exposed accessible active sites, and the internal voids can guarantee sufficient contact of reactants and catalysts. In this work, a unique yolk-shell structured nanoreactor Au@Co3O4/CeO2@mSiO2 was fabricated and applied as nanozyme for biosensing. The Au@Co3O4/CeO2@mSiO2 exhibited superior peroxidase-like activity with a lower Michaelis constant (Km) and a higher affinity to H2O2. The enhanced peroxidase-like activity was attributed to the unique structure and the synergistic effects between the multiple active components. Colorimetric essays were developed based on Au@Co3O4/CeO2@mSiO2 for the ultra-sensitive sensing of glucose in the range of 3.9 nM-1.03 mM with the limit of detection as low as 3.2 nM. In the detection of glucose-6-phosphate dehydrogenase (G6PD), the cooperation between G6PD and Au@Co3O4/CeO2@mSiO2 triggered the redox cycling between NAD+ and NADH, thereby achieving the amplification of the signal and enhancing the sensitivity of the assay. The assay showed superior performance as compared to other methods with linear response of 5.0 × 10-3-15 mU mL-1 and lower detection limit of 3.6 × 10-3 mU mL-1. The fabricated novel multi-enzyme catalytical cascade reaction system allowed rapid and sensitive biodetection, demonstrating its potential in biosensors and biomedical applications.

Abundance and characteristics of microplastics in the Wanquan River estuary, Hainan Island.

As the nexus where rivers and oceans meet, estuaries are vulnerable to microplastic (MP) pollution derived from rivers. However, few studies have focused on the pollution status of MPs in small estuarine areas. Here, the abundance and characteristics of MPs in surface water and sediment samples from a small estuary, the Wanquan River estuary, were studied. The average abundance of MPs was 6573 ± 2659 n/m3 in surface water and 1065 ± 696 n/kg dw in sediment samples from the Wanquan River estuary. Most of the MPs in water samples and sediments were red (92.9 % and 88.1 %) fragments (87.4 % and 95.5 %) with sizes <1.0 mm (90.8 % and 92.4 %) made up of antifouling paint particles (APPs) (83.5 % and 89.8 %), respectively. A significant positive correlation (p < 0.01) was found between the concentration of Cu2+ and the abundance of APPs in sediment samples from the Wanquan River estuary. The APPs in the sediments can act as a continuous source of toxic chemicals (e.g., Cu2+) to marine environments. The results of this study expand our knowledge about MP pollution in small estuaries, and the ecological risk of APPs in the Wanquan River estuary to aquatic organisms should not be ignored.

Biotic resistance to fish invasions in southern China: Evidence from biomass, habitat, and fertility limitation.

Understanding the mechanisms underlying the invasion success or failure of alien species can help to predict future invasions and cope with the invaders. The biotic resistance hypothesis posits that diverse communities are more resistant to invasion. While many studies have examined this hypothesis, the majority of them have focused on the relationship between alien and native species richness in plant communities, and results have often been inconsistent. In southern China, many rivers have been invaded by alien fish species, providing an opportunity to test the resistance of native fish communities to alien fish invasions. Using survey data for 60,155 freshwater fish collected from five main rivers of southern China for 3 years, we assessed the relationships between native fish richness and the richness and biomass of alien fishes at river and reach spatial scales, respectively. Based on two manipulative experiments, we further examined the impact of native fish richness on habitat selection and the reproductive ability of an exotic model species Coptodon zillii. We found no apparent relationship between alien and native fish richness, whereas the biomass of alien fish significantly decreased with increasing native fish richness. In experiments, C. zillii preferred to invade those habitats that had low native fish richness, given evenly distributed food resources; reproduction of C. zillii was strongly depressed by a native carnivorous fish Channa maculata. Together, our results indicate that native fish diversity can continue to provide biotic resistance to alien fish species in terms of limiting their growth, habitat selection, and reproduction when these aliens have successfully invaded southern China. We thus advocate for fish biodiversity conservation, especially for key species, to mitigate against the population development and ecological impact of alien fish species.

Light-enhanced transparent hydrogel for uric acid and glucose detection by four different analytical platforms.

The lack of solid-phase media limits the portability of colorimetric sensing platforms. In this study, a series of transparent polyvinyl alcohol (PVA) hydrogels encapsulated antimony tin oxide nanoparticles (ATO NPs) and 3,3',5,5'-tetramethylbenzidine (TMB) were developed as the solid-phase sensing media for glucose and uric acid. Under the conditions of H2O2 and UV light, the hydrogel presented a multicatalytic ability (photo Fenton-like and peroxidase-like activities), which accelerated the oxidation of TMB, turning the hydrogel from colorless to blue and finally enhancing the detection signal. The plasticity of the hydrogel allowed it to be designed into various shapes (membrane, microsphere etc.) to adapt multiple detection platforms (a liquid/solid-phase UV spectrophotometer, a NanoPhotometer, and smartphone spectroscopy). The hydrogel sensing media exhibited excellent tunability and enhanced the photocatalytic ability. The proposed material was successfully applied to detect glucose and uric acids in real samples by four detection platforms to evaluate its practicability.

An integrative investigation of developmental toxicities induced by triphenyltin in a larval coral reef fish, Amphiprion ocellaris.

Triphenyltin (TPT) is widely distributed on coastlines, which makes coral reef fish a potential target of TPT pollution. However, the negative effects of TPT on coral reef fish remain poorly understood. Therefore, in the present study, the larval coral reef fish Amphiprion ocellaris was used to investigate the developmental toxicities of TPT at environmentally relevant concentrations (0, 1, 10 and 100 ng/L). After TPT exposure for 14 d, the cumulative mortality increased, and growth was suppressed. In addition, TPT exposure inhibited the development of melanophores and xanthophores and delayed white strip formation, which might be responsible for the disruption of the genes (erbb3b, mitfa, kit, xdh, tyr, oca2, itk and trim33) related to pigmentation. TPT exposure also attenuated ossification of head skeletal elements and the vertebral column and inhibited the expression of genes (bmp2, bmp4 and sp7) related to skeletal development. The observed developmental toxicities on growth, pigmentation and skeleton development might be associated with the disruption of thyroid hormones and the genes related to thyroid hormone regulation (tshß, thrα, thrß, tg, tpo, dio2, and ttr). In addition, TPT exposure interfered with locomotor and shoaling behavior, and the related genes dbh, avp and avpr1aa. Taken together, our results suggest that TPT pollution might threaten the development of one of the most iconic coral reef fish, which might produce disastrous consequences on the health of coral reef ecosystems.

Low-Valent Tungsten-Catalyzed Controllable Oxidative Dehydrogenative Coupling of Anilines.

Herein, we have developed an efficient tungsten-catalyzed homogeneous system for oxidative dehydrogenative coupling of anilines to selectively produce various azoaromatics and azoxyaromatics as well as 2-substituted indolone N-oxides by simply regulating the reaction solvent with peroxide as a terminal oxidant under additive-free conditions. These findings provide an experimental framework for exploring tungsten catalysis in organic synthesis and offer an efficient and convenient tactic for the selective oxidation of anilines.

Triphenyltin Influenced Carotenoid-Based Coloration in Coral Reef Fish, Amphiprion ocellaris, by Disrupting Carotenoid Metabolism.

Triphenyltin (TPT), a kind of persistent pollutant, is prevalent in the aquatic environment and could pose a threat to coral reef fish. However, little is known about the toxicity of TPT on coral reef fish, especially regarding the representative characteristics of body coloration. Therefore, this study chose the clownfish (Amphiprion ocellaris) in order to investigate the effects of TPT exposure on its carotenoid-based body coloration under the environmentally relevant concentrations (0, 1, 10 and 100 ng/L). After TPT exposure for 60 d, the carotenoid contents were decreased and histological damage in the liver was found, shown as nuclear pyknosis and shift, lipid deposition and fibrotic tissue hyperplasia. Liver transcriptomic analysis showed that TPT exposure interfered with oxidative phosphorylation and fatty acid metabolism pathways, which related to carotenoids uptake and metabolism. Furthermore, TPT exposure led to oxidative damage in the liver, which is responsible for the changes in the antioxidant capacity of enzymes, including GSH, MDA, POD, CAT and T-SOD. TPT exposure also affected the genes (Scarb1, CD36, Stard3 and Stard5) related to carotenoid absorption and transport, as well as the genes (GstP1 and Bco2) related to carotenoid deposition and decomposition. Taken together, our results demonstrate that TPT influenced carotenoid-based coloration in coral reef fish by disrupting carotenoid metabolism, which complements the ecotoxicological effects and toxic mechanisms of TPT and provides data for the body color biology of coral reef fishes.

Thymic lipofibroadenoma of the anterior mediastinum: A rare case report.

BACKGROUND: Lipofibroadenoma is an extremely rare thymic tumor, and the anterior mediastinum is the most common site. CASE SUMMARY: A 21-year-old male was admitted with fever without obvious cause for 2 months. After admission, the patient's highest temperature was 38.3°C, accompanied by diarrhea. Physical examination showed coarse breath sounds in both lungs. Chest enhanced computed tomography (CT) showed a mass of mixed density shadow on the left side of the anterior mediastinum with a size of approximately 9.2 cm × 5 cm × 2.1 cm and a clear boundary mixed with a low fat density shadow. Mediastinal tumors were removed under general anesthesia by video-assisted thoracoscopic surgery. Macroscopically, a clear boundary was shown between the tumor and the remaining thymus. Microscopically, the tumor contained a large amount of mature adipose and fibrous tissue with scattered cord-like epithelial tissue and a small number of lymphocytes scattered in the stroma. The tumor lacked thymic bodies. The neoplastic epithelial cells were oval or polygonal and arranged in fissures, the nuclei were uniform in size and mild in shape, and mitosis was rare. Epithelial cells were positive for AE1/AE3 and CK19, lymphocytes were positive for CD3 and CD20, and fat and fibrous tissue were positive for S-100 and vimentin, respectively. The Ki67 labeling index was less than 5%. Based on histological features and immunophenotype, thymic lipofibroadenoma was diagnosed. The patient was followed up 1 year after the operation, and no recurrence or residual lesions were found on the X-ray re-examination. CONCLUSION: Lipofibroadenoma is a benign thymic tumor, and thymectomy is regarded as the best treatment. The biological behavior of thymic lipofibroadenoma is good, and the recurrence rate is low.

Pseudo-mono-axial ligand fields that support high energy barriers in triangular dodecahedral Dy(iii) single-ion magnets.

The synthesis of air-stable, high-performance single-molecule magnets (SMMs) is of great significance for their practical applications. Indeed, Ln complexes with high coordination numbers are satisfactorily air stable. However, such geometries easily produce spherical ligand fields that minimize magnetic anisotropy. Herein, we report the preparation of three air-stable eight-coordinate mononuclear Dy(iii) complexes with triangular dodecahedral geometries, namely, [Dy(BPA-TPA)Cl](BPh4)2 (1) and [Dy(BPA-TPA)(X)](BPh4)2·nCH2Cl2 (X = CH3O- and n = 1 for 2; L = PhO- and n = 2 for 3), using a novel design concept in which the bulky heptadentate [2,6-bis[bis(2-pyridylmethyl)amino]methyl]-pyridine (BPA-TPA) ligand enwraps the Dy(iii) ion through weak coordinate bonds leaving only a small vacancy for a negatively charged (Cl-), methoxy (CH3O-) or phenoxy (PhO-) moiety to occupy. Magnetic measurements reveal that the single-molecule magnet (SMM) property of complex 1 is actually poor, as there is almost no energy barrier. However, complexes 2 and 3 exhibit fascinating SMM behavior with high energy barriers (U eff = 686 K for 2; 469 K for 3) and magnetic hysteresis temperatures up to 8 K, which is attributed to the pseudolinear ligand field generated by one strong, highly electrostatic Dy-O bond. Ab initio calculations were used to show the apparent difference in the magnetic dynamics of the three complexes, confirming that the pseudo-mono-axial ligand field has an important effect on high-performance SMMs compared with the local symmetry. This study not only presents the highest energy barrier for a triangular dodecahedral SMM but also highlights the enormous potential of the pseudolinear Dy-L ligand field for constructing promising SMMs.

Genetic Structure of an East Asian Minnow (Toxabramis houdemeri) in Southern China, with Implications for Conservation.

River dynamics have been hypothesized to substantially influence the genetic structure of freshwater fish taxa. Southern China harbors abundant independent river systems, which have undergone historical rearrangements. This river system is thus an excellent model with which to test the abovementioned hypothesis. In this study, a cyprinid widespread in many independent rivers in southern China, Toxabramis houdemeri, was chosen as an exemplar species with which to explore the effects of river configuration changes on spatial genetic structure using mitochondrial and nuclear markers. The results indicated that the T. houdemeri populations fell into four mitochondrial haplotype groups, each genetically endemic to a single river or two adjacent river systems. The mitochondrial haplotype network recovered a clear genetic boundary between Hainan Island populations and mainland populations. Notable genetic differentiation was observed within populations from distinct river systems in both mitochondrial and nuclear loci. River system separation, mountain barriers, and mobility were the key factors shaping the genetic structure of T. houdemeri populations. Late Pleistocene divergence and historical immigration were identified within the four mitochondrial haplotype groups, indicating that river rearrangements triggered by the Late Pleistocene glacial cycles were important drivers of the complex genetic structure and demographic history of T. houdemeri. Historical demographics suggested that T. houdemeri populations expanded during the Late Pleistocene. The present study has important consequences for the management and conservation of T. houdemeri.

Effects of Glucocorticoids on Postoperative Neurocognitive Disorders in Adult Patients: A Systematic Review and Meta-Analysis.

Background: Postoperative neurocognitive disorders (PNDs) is common among surgical patients, however, the effect of glucocorticoids for preventing PNDs is not clear. This review aims to evaluate the effect of glucocorticoids on the incidence of PNDs in adult patients undergoing surgery. Methods: The databases of PubMed/Medline, Embase, the Cochrane Library, and Web of science were searched for all available randomized controlled trials (RCTs) from inception to April 30, 2022. RCTs comparing the effect of glucocorticoids with placebo on the incidence of PNDs in adult surgical patients (≥18 years old) were eligible. Subgroup analyses and meta-regressions were performed to evaluate sources of clinical heterogeneity. The level of certainty for main outcomes were assessed by the Grading of Recommendations Assessment, Development and Evaluation (GRADE) methodology. Results: Eleven trials with a total of 10,703 patients were identified. Compared with the control group, glucocorticoids did not reduce the incidence of PNDs (RR: 0.84, 95% CI: 0.67 to 1.06, P = 0.13, GRADE = moderate). Secondary analyses for primary outcome did not change the result. In addition, the length of ICU stay was decreased in glucocorticoids group (RR: -13.58, 95% CI: -26.37 to -0.80, P = 0.04, GRADE = low). However, there were no significant differences between groups with regards to the incidence of postoperative infection (RR: 0.94, 95% CI: 0.84 to 1.06, P = 0.30, GRADE = moderate), blood glucose level (RR: 1.05, 95% CI: -0.09 to 2.19, P = 0.07, GRADE = low), duration of mechanical ventilation (RR: -2.44, 95% CI: -5.47 to 0.59, P = 0.14, GRADE = low), length of hospital stay (RR: -0.09, 95% CI: -0.27 to 0.09, P = 0.33, GRADE = moderate) and 30-day mortality (RR: 0.86, 95% CI: 0.70 to 1.06, P = 0.16, GRADE = moderate). Conclusions: This meta-analysis suggests that perioperative administration of glucocorticoids may not reduce the incidence of PNDs after surgery. The effect of glucocorticoids on decreased length of ICU stay needs further researches. Future high-quality trials using acknowledged criteria and validated diagnostic tools are needed to determine the influence of glucocorticoids on long-term PNDs. Systematic Review Registration: https://www.crd.york.ac.uk/prospero/display_record.php?ID=CRD42022302262, identifier: CRD42022302262.

Factors affecting microplastic accumulation by wild fish: A case study in the Nandu River, South China.

Quantifying microplastic accumulation in aquatic organisms is important for risk assessments in natural habitats. However, studies on the factors influencing microplastic accumulation by fish, particularly in natural water bodies, remain limited. In this study, we monitored the microplastic pollution characteristics in the fish digestive tract and surface water of the Nandu River, the largest river in Hainan, China. Among the 179 fish examined, microplastics were detected in 90.5 %, covering 27 fish species. Moreover, low abundance of microplastics occurred among the different fish, with an average of 3.20 ± 2.60 particles per fish. Fibrous microplastics with a large size (>500 µm) were dominant in both the water column and fish. In this study, fish size, feeding habits, and living habitats did not affect microplastic abundance in fish. Based on the analysis of differences in the abundance and morphological characteristics of microplastics in water column and fish, we suggested that the random intake and differential excretion of microplastics with different characteristics by fish might lead to the homogeneity of microplastic accumulation in different fish. Our study suggest that more attention should be given to the negative effects of microplastics on small fish owing to the higher microplastic exposure per gram weight, and further improvement in microplastic risk assessment methods is required.

Large-scale DNA barcoding of the subfamily Culterinae (Cypriniformes: Xenocyprididae) in East Asia unveils a geographical scale effect, taxonomic warnings and cryptic diversity.

Geographical scale might be expected to impact significantly the efficiency of DNA barcoding as spatially comprehensive sampling provides opportunities to uncover intricate relationships among closely related species and to detect cryptic diversity for widespread taxa. Here, we present a DNA barcoding study on a Xencyprididae subfamily (Culterinae) involving the production of 998 newly generated DNA barcodes from East Asian drainages (80 localities). Together with 513 barcodes mined from BOLD and GenBank, a reference library consisting of 1511 DNA barcodes (116 localities) for 42 species was assembled, accounting for 66% of known Culterinae species. Intraspecific genetic distances are positively correlated to geographical scale, while a negative correlation is detected between interspecific genetic distances and geographical scale. The present study demonstrates that geographical scale influences the efficiency of DNA barcoding by narrowing the width of the barcoding gap. DNA-based species delimitation analyses delimited 44 molecular operational taxonomic units (MOTUs). Rampant cryptic diversity is detected within eight species with multiple MOTUs, whereas 25 species present mismatch between morphological and molecular delimitations. A total of 18 species are lumped into nine MOTUs due to low interspecific divergence and/or mixed lineages. Several MOTU divergences are hypothesized to relate to known biogeographical barriers and geological events during the Pliocene and Pleistocene. This study provides new insights into the taxonomy and phylogeography of the subfamily Culterinae.

Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics.

Triggering C-N bond formation with nitroaromatics and boronic acids at mild conditions is highly desirable, since most prior works were carried out under harsh conditions and sometimes suffered from poor chemo- or regioselectivity. Herein, a low-valent-tungsten-catalyzed reaction that enables the ambient temperature amination of boronic acids with nitroaromatics is disclosed. With readily available W(CO)6 as a precatalyst under external-photosensitizer-free conditions, nitroaromatics smoothly undergo C-N coupling reactions with their boronic acid partners, delivering structurally diverse secondary amines in good yields (>50 examples, yields up to 96%). This methodology is both scalable and highly chemoselective and engages both aliphatic and aromatic boronic acid partners. The catalysis is initiated by the deoxygenation of nitroaromatics by a trans-[W(CO)4(PPh3)2] (trans-W, PPh3 = triphenylphosphine) complex, which forms in situ via ligand replacement.