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Introduction: Existing research has shown that intimate partner violence (IPV) may hinder maternal access to healthcare services, thereby affecting maternal and child health. However, current studies have ignored whether emotional intimate partner violence (EV) could negatively affect maternal healthcare use. This study aims to evaluate the impact of invisible IPV on maternal healthcare utilization in Pakistan. Methods: We analyzed nationally representative data from the Pakistan Demographic and Health Survey database from 2012–2013 and 2017–2018. Exposure to physical intimate partner violence (PV) and EV was the primary predictor. Based on women's last birth records, outcomes included three binary variables indicating whether women had inadequate antenatal care (ANC) visits, non-institutional delivery, and lack of postnatal health check-ups. A logistic regression model was established on weighted samples. Results: Exposure to EV during pregnancy was significantly associated with having inadequate ANC visits (aOR = 2.16, 95% CI: 1.06 to 4.38, p = 0.033) and non-institutional delivery (aOR = 2.24, 95% CI: 1.41 to 3.57, p = 0.001). Lifetime exposure to EV was associated with increased risks of inadequate ANC visits (aOR = 1.48, 95% CI: 1.00 to 2.19, p = 0.049). Lifetime exposure to low-scale physical intimate partner violence (LSPV) (adjusted OR (aOR) = 1.73, 95% CI: 1.29 to 2.31, p < 0.001) was associated with increased risks of having no postnatal health check-ups. Conclusions: Pregnant women who experienced EV and LSPV are at greater risk of missing maternal healthcare, even if the violence occurred before pregnancy. Therefore, in countries with high levels of IPV, early screening for invisible violence needs to be integrated into policy development, and healthcare providers need to be trained to identify EV and LSPV. [ABSTRACT FROM AUTHOR]

Asymmetric catalytic carbene reactions have been well documented in the last few decades for the expeditious assembly of chiral molecules with structural diversity. However, the enantioselective construction of all‐carbon quaternary centers remains a challenge in this area. In this review article, two types of asymmetric carbene reactions that beyond cyclopropanation, cyclopropenation, and Büchner reaction, have been summarized for the construction of all‐carbon quaternary centers: 1) using carbene species as a 1C synthon that reacts with a trisubstituted prochiral center; 2) sequential installation of two different C−C bonds on the carbene position, which features a gem‐difunctionalization reaction. Especially, the asymmetric metal carbene gem‐dialkylation process, which has emerged as a practical and versatile method for the expeditious assembly of complex architectures from readily available chemical resources, is a complementary approach for the expeditious assembly of all‐carbon quaternary centers. [ABSTRACT FROM AUTHOR]

Semen cuscutae is a well-known Chinese medicine which has been used to nourish kidney. It is the first study to demonstrate that the polysaccharides from semen cuscutae showed significant activity of nourishing kidney-yang by increasing the levels of testosterone and estradiol, decreasing the level of blood urea nitrogen, improving immune function, possessing antioxidant effect. Three homogeneous polysaccharides were obtained by DEAE-cellulose and Sephacryl S-400 which were named as C-7WR1, C-7WR2 and C-7WR3 with average molecular weight of 7.59 × 10 4 , 3.23 × 10 4 and 2.25 × 10 4 respectively. C-7WR1 was composed of fructose: mannose = 0.02:1. C-7WR2 was composed of fructose: mannose: xylose: arabinose = 0.01:1:0.14:0.33. C-7WR3 was composed of fructose: mannose: xylose: arabinose = 0.01:1:0.10:0.47. They mainly contained mannose. Their fourier transform infrared features were similar. They all had no nucleic acid and protein. [ABSTRACT FROM AUTHOR]

The combination of two or more unsaturated structuralunits toform cyclic organic compounds is commonly referred to as cycloaddition,and the combination of two unsaturated structural units that formsa six-membered ring is formally either a [5 + 1]-, [4 + 2]-, [2 +2 + 2]-, or [3 + 3]-cycloaddition. Occurring as concerted or stepwiseprocesses, cycloaddition reactions are among the most useful syntheticconstructions in organic chemistry. Of these transformations, theconcerted [4 + 2]-cycloaddition, the Diels–Alder reaction,is by far the best known and most widely applied. However, althoughsymmetry disallowed as a concerted process and lacking certifiableexamples until recently, stepwise [3 + 3]-cycloadditions offer advantagesfor the synthesis of a substantial variety of heterocyclic compounds,and they are receiving considerable attention. [ABSTRACT FROM AUTHOR]

Diazo compounds have been used as precursors to a wide variety of heterocyclic compounds that represent the core structural subunits in many biologically active compounds. Various methodologies have been established for their synthesis via metal-catalyzed carbene transformations. Although the advantages of vinyldiazoacetates have been known for many years, realization of the synthetic use of enoldiazoacetates has been more recent. This review covers advances in the utility of silyl-protected enoldiazoacetates in heterocycle syntheses that include X-H insertion reactions, ylide rearrangements, formal [3+3]- and [4+3]-cycloaddition reactions, and other traditional and unusual metal carbene transformations. [ABSTRACT FROM AUTHOR]

Die Abspaltung von Distickstoff aus Enoldiazoacetaten mithilfe eines RhII ‐ Katalysators erzeugt Metallenolcarbene, deren anschließende vinyloge Addition an N ‐ Acyliminopyridinium ‐ Ylide in einer effektiven formalen [3+3] ‐ Cycloaddition resultiert. Hoch substituierte 1,2,3,6 ‐ Tetrahydropyridazine werden so in hohen Ausbeuten und bis 98 % ee erhalten. [ABSTRACT FROM AUTHOR]

Extrusion of dinitrogen from enol diazoacetates with a RhII catalyst generates metal enol carbenes. Subsequent vinylogous addition of these to N‐acyliminopyridinium ylides results in an effective formal [3+3] cycloaddition to give highly substituted 1,2,3,6‐tetrahydropyridazines in up to 98 % ee and high yield. [ABSTRACT FROM AUTHOR]

Silyl-protected enol diazoacetates undergo dirhodium(II)-catalyzed reactions with nitrile oxides to form acid-labile ketenimines via dipolar cycloaddition of nitrile oxides to a donor/acceptor cyclopropene and Lossen rearrangement of the dipolar adduct; acid catalysis converts the ketenimine to the furan product. [ABSTRACT FROM AUTHOR]

Abstract: DMDO oxidation of functionalized α-diazo-β-ketoacetates, formed by zinc triflate catalyzed Mukaiyama-aldol condensation of methyl diazoacetoacetate with aldehydes, occurred in quantitative yield to form dihydrofuranols that undergo acid catalyzed dehydration under mild conditions to generate 3-methoxyfuran-2-carboxylates in good yield. [Copyright &y& Elsevier]

Metal carbene transfer reactions have been well-established as an indispensable tool in modern organic synthesis, especially in the construction of C–C and C–X bonds with high efficiency and selectivity. Among these, stepwise carbene transfer reaction with alkenes beyond classical cyclopropanation reaction has been demonstrated as a practical method for the effective olefinic C–H/C–C bond functionalization. This review highlights the recent achievements in this area for the direct C–C bond formation involving metal carbene species with alkenes through a through stepwise reaction pathway. The content of this review is organized into three general categories according to the types of the reactions, including (i) direct nucleophilic addition of alkenes with metal carbene species, (ii) cross-coupling reaction via an alkenylic C–H bond activation and migration insertion sequence, and (iii) catalytic coupling reaction involving radical intermediate. Considering this rapidly evolving field, detailed reaction mechanism, current limitations, and future research directions are discussed. 1 Introduction 2 Nucleophilic Addition of Alkenes to Metal Carbene Species 2.1 Using Polarized Alkenes 2.2 Using Unactivated Alkenes 2.3 Cascade Reactions 3 Cross-Coupling Reaction Involving Metal Carbene Migratory Insertion Process 4 Coupling Reaction Involving Radical Intermediate 5 Conclusions and Perspectives [ABSTRACT FROM AUTHOR]

Silver(i)-catalyzed asymmetric formal [3+3]-cycloaddition of nitrones with a donor–acceptor cyclopropene, formed in situ from dirhodium acetate-catalyzed dinitrogen extrusion/intramolecular cyclization of enoldiazoacetates, effectively generates 3,6-dihydro-1,2-oxazine derivatives in high yield and with exceptional stereocontrol. [ABSTRACT FROM AUTHOR]

A highly diastereoselective formal [3+2+1]-cycloaddition reaction that produces multi-functionalized bicyclic pyrazolidinone derivatives is achieved in moderate to high yield by Rh2(4S-MPPIM)4-catalyzed reaction of azomethine imines with two molecules of a diazo ketone. [ABSTRACT FROM AUTHOR]

A highly enantioselective three-component reaction of a diazoacetophenone, an alcohol, and an imine catalyzed cooperatively by Rh2(OAc)4and BINOL-derived chiral phosphoric acid has been developed for the synthesis of chiral β-amino-α-hydroxyl ketones in good yield with excellent diastereo and enantio selectivity. [ABSTRACT FROM AUTHOR]

As one of the abundant and inexpensive metals on the earth, copper has demonstrated broad applications in synthetic chemistry and catalysis. Among these copper-catalyzed advances, copper carbenes are versatile and reactive intermediates that can mediate a variety of transformations, which have attracted much attention in the past decades. The present review summarizes two different reaction models that take place between a copper carbene intermediate and alkyne species, including the cross-coupling reaction of copper carbene intermediate with terminal alkyne, and the addition of copper carbene intermediate onto the C–C triple bond. This article will cover the profile from 2010 to 2021 by placing emphasis on the detailed catalytic models and highlighting the synthetic applications offered by these practical and mild methods. [ABSTRACT FROM AUTHOR]

A regio‐ and stereoselective stepwise (4+2) annulation of N‐propargylamides and α,β‐unsaturated imines/ketones has been accomplished with synergetic catalysis by a combination of a gold‐complex and a chiral quinine‐derived squaramide (QN‐SQA), leading to highly functionalized chiral tetrahydropyridines/dihydropyrans in good to high yields with generally excellent enantioselectivity. Mechanistic studies and DFT calculations indicate that the in situ formed alkylgold species is the key intermediate in this transformation, and the amide group served as a traceless directing group in this highly selective transformation. This method complements the enantioselective (4+2) annulation of allene reagents, providing the formal internal C−C π‐bond cycloaddition products, which is challenging and remains elusive. [ABSTRACT FROM AUTHOR]

A regio‐ and stereoselective stepwise (4+2) annulation of N‐propargylamides and α,β‐unsaturated imines/ketones has been accomplished with synergetic catalysis by a combination of a gold‐complex and a chiral quinine‐derived squaramide (QN‐SQA), leading to highly functionalized chiral tetrahydropyridines/dihydropyrans in good to high yields with generally excellent enantioselectivity. Mechanistic studies and DFT calculations indicate that the in situ formed alkylgold species is the key intermediate in this transformation, and the amide group served as a traceless directing group in this highly selective transformation. This method complements the enantioselective (4+2) annulation of allene reagents, providing the formal internal C−C π‐bond cycloaddition products, which is challenging and remains elusive. [ABSTRACT FROM AUTHOR]

A robust and practical difluoroalkylation synthon, α,α‐difluoroenol species, which generated in situ from trifluoromethyl diazo compounds and water in the presence of dirhodium complex, is disclosed. As compared to the presynthesized difluoroenoxysilane and in situ formed difluoroenolate under basic conditions, this difluoroenol intermediate displayed versatile reactivity, resulting in dramatically improved enantioselectivity under mild conditions. As demonstrated in catalytic asymmetric aldol reaction and Mannich reactions with ketones or imines in the presence of chiral organocatalysts, quinine‐derived urea, and chiral phosphoric acid (CPA), respectively, this relay catalysis strategy provides an effective platform for applying asymmetric fluorination chemistry. Moreover, this method features a novel 1,2‐difunctionalization process via installation of a carbonyl motif and an alkyl group on two vicinal carbons, which is a complementary protocol to the metal carbene gem‐difunctionalization reaction. [ABSTRACT FROM AUTHOR]

A synergistic rhodium‐ and Brønsted acid‐ catalyzed reaction of quinone imine ketals with diazo compounds to access multi‐substituted anilines is presented here. This reaction takes place through a process involving C−O bond cleavage, modification of the leaving alcoholic fragment, and selective reassembly of the reactive fragments. Moderate enantioselectivities are achieved when a chiral 1,1'‐bi(2‐naphthol)‐based phosphoric acid is used. [ABSTRACT FROM AUTHOR]

An abstract of the article "Enantioselective cis-β-Lactam Synthesis by Intramolecular C-H Functionalization from Enoldiazoacetamides and Derivative Donor-Acceptor Cyclopropenes" by X. Xu and colleagues is presented.

An abstract of the article "Straightforward Access to the [3.2.2]Nonatriene Structural Framework via Intramolecular Cyclopropenation/Buchner Reaction/Cope Rearrangement Cascade" is presented.

Ethnopharmacological relevance Arecae semen, the ripe seed of Areca catechu L., has been used as vermifuge and digestant in traditional Chinese medicine (TCM). However, the potential toxicity effect of arecae semen has not been completely investigated. The aim of the study The present study was aimed at evaluating the sub-chronic toxicity of arecae semen by oral administration in Wistar rats. Materials and methods A total of 120 Wistar rats were randomly divided into 4 groups (15 males and 15 females per group). The treated groups were given arecae semen aqueous extract (ASAE) at the dose of 750, 1500 and 4500 mg/kg/day by oral administration respectively, and the control group was received distilled water only. The rats and their consumed feed were weighted every 3 days. The clinical changes and mortality were observed and recorded daily. Hematological parameters, biochemical parameters, organ weights, urinalysis and histopathological examination of all rats were tested at the end of the 30-day treatment period and another 10-day recovery period. Results Deaths, weight loss, diarrhea, sluggish action, tremors and body curl up were observed in the 1500 and 4500 mg/kg groups during the study. The relative organ weights of liver and testis in male rats of 4500 mg/kg group were significantly different compared with the control group at the end of the treatment period. As for laboratory parameters, there were no significant differences at the dose of 1500 and 4500 mg/kg groups compared with the control group in the study, except the white blood cell count (WBC), aspartate aminotransferase (AST), alanine aminotransferase (ALT), albumin (ALB), blood urea nitrogen (BUN), creatinine (Cr), glucose (GLU) and total cholesterol (CHOL). In addition, the results of histopathological examination and feed intake showed no significant difference compared with the control group. Conclusions The results showed that ASAE at the dose of 750 mg/kg/day was safe, but long-term oral administration of ASAE with high dosage was toxic. Moreover, the toxic ingredients of ASAE including arecoline, and also some other compounds should be researched. [ABSTRACT FROM AUTHOR]

Review: 91 refs. [ABSTRACT FROM AUTHOR]

Extrusion of dinitrogen from enol diazoacetates with a Rh(II) catalyst generates metal enol carbenes. [ABSTRACT FROM AUTHOR]

Ag(I)-catalyzed asymmetric formal [3 + 3]-cycloaddition of nitrones (III) to the donor-acceptor substituted cyclopropene (II) affords 3,6-dihydro-1,2-oxazine derivatives (IV) (19 examples) in high yields with exceptional stereocontrol. [ABSTRACT FROM AUTHOR]

Iron(III) chloride catalyzes the aerobic oxidation of tertiary anilines, including N-aryltetrahydroisoquinolines, to form reactive iminium ion intermediates that undergo Mannich reactions with silyloxyfurans, nitroalkanes, and other nucleophiles to give the corresponding butenolides, nitro compounds, and α-substituted tetrahydroisoquinolines, respectively. [ABSTRACT FROM AUTHOR]

The catalytic asymmetric construction of all‐carbon quaternary stereocenters has received tremendous interest over the past decades, and numerous efficient protocols have been disclosed based on the formation of one C−C bond between two assembling reactants. However, the use of asymmetric multi‐component reactions that build two C−C bonds on the same carbonic center with concomitant assembly of quaternary stereocenters is rare and remains challenging. Herein, we disclose an enantioselective three‐component reaction of α‐diazo ketones with alkenes and 1,3,5‐triazines under dirhodium/chiral phosphoric acid cooperative catalysis, which leads to a practical and atom‐economic synthesis of poly‐functionalized chiral ketones that bear a α‐quaternary stereocenter in generally good to high yields with excellent enantioselectivities. In comparison to the previous method for the construction of tertiary and quaternary stereocenters via carbene gem‐difunctionalization reactions, this reaction features an unprecedented gem‐dialkylation process via sequential installation of two C−C bonds on the carbene center in one reaction, providing an essential complement to the asymmetric construction of all‐carbon quaternary stereocenters using common and readily available starting materials. [ABSTRACT FROM AUTHOR]

The catalytic asymmetric construction of all‐carbon quaternary stereocenters has received tremendous interest over the past decades, and numerous efficient protocols have been disclosed based on the formation of one C−C bond between two assembling reactants. However, the use of asymmetric multi‐component reactions that build two C−C bonds on the same carbonic center with concomitant assembly of quaternary stereocenters is rare and remains challenging. Herein, we disclose an enantioselective three‐component reaction of α‐diazo ketones with alkenes and 1,3,5‐triazines under dirhodium/chiral phosphoric acid cooperative catalysis, which leads to a practical and atom‐economic synthesis of poly‐functionalized chiral ketones that bear a α‐quaternary stereocenter in generally good to high yields with excellent enantioselectivities. In comparison to the previous method for the construction of tertiary and quaternary stereocenters via carbene gem‐difunctionalization reactions, this reaction features an unprecedented gem‐dialkylation process via sequential installation of two C−C bonds on the carbene center in one reaction, providing an essential complement to the asymmetric construction of all‐carbon quaternary stereocenters using common and readily available starting materials. [ABSTRACT FROM AUTHOR]

The Rh-catalyzed title reaction followed by Lewis acid-mediated cyclization allows an efficient and regiospecific access to polysubstituted pyrazoles. [ABSTRACT FROM AUTHOR]

as a route for the highly diastereoselective synthesis of multi-functionalized bicyclic pyrazolidinone derivatives (III) (11 examples) [ABSTRACT FROM AUTHOR]

A series of 4-styryl-5-methoxyoxazoles (III) is readily prepared by reaction of styryl diazoacetate (I) with aryl oximes (II). [ABSTRACT FROM AUTHOR]

The synthesis of the heterocyclic skeleton proceeds with good to excellent stereoselectivity. [ABSTRACT FROM AUTHOR]

Rare ginsenosides are the major components of red ginseng. However, there has been little research into the relationship between the structure of ginsenosides and their anti-inflammatory activity. In this work, BV-2 cells induced by lipopolysaccharide (LPS) or nigericin, the anti-inflammatory activity of eight rare ginsenosides, and the target proteins expression of AD were compared. In addition, the Morris water maze test, HE staining, thioflavins staining, and urine metabonomics were used to evaluate the effect of Rh4 on AD mice. Our results showed that their configuration influences the anti-inflammatory activity of ginsenosides. Ginsenosides Rk1, Rg5, Rk3, and Rh4 have significant anti-inflammatory activity compared to ginsenosides S-Rh1, R-Rh1, S-Rg3, and R-Rg3. Ginsenosides S-Rh1 and S-Rg3 have more pronounced anti-inflammatory activity than ginsenosides R-Rh1 and R-Rg3, respectively. Furthermore, the two pairs of stereoisomeric ginsenosides can significantly reduce the level of NLRP3, caspase-1, and ASC in BV-2 cells. Interestingly, Rh4 can improve the learning ability of AD mice, improve cognitive impairment, reduce hippocampal neuronal apoptosis and Aβ deposition, and regulate AD-related pathways such as the tricarboxylic acid cycle and the sphingolipid metabolism. Our findings conclude that rare ginsenosides with a double bond have more anti-inflammatory activity than those without, and 20(S)-ginsenosides have more excellent anti-inflammatory activity than 20(R)-ginsenosides. [ABSTRACT FROM AUTHOR]

An oxidative strategy is reported to access α‐oxo BMIDA gold carbenes directly from BMIDA‐terminated alkynes. Besides offering expedient access to seldom studied boryl metal carbenes, these BMIDA gold carbene species undergo facile insertions into methyl, methylene, methine, and benzylic C−H bonds in the absence of the Thorpe–Ingold effect. They also undergo efficient OH insertion, cyclopropanation, and F−C alkylations. This chemistry provides rapid access to structurally diverse α‐BMIDA ketones, which are scarcely documented. In combination with DFT studies, the role of BMIDA is established to be an electron‐donating group that attenuates the high electrophilicity of the gold carbene center. [ABSTRACT FROM AUTHOR]

An oxidative strategy is reported to access α‐oxo BMIDA gold carbenes directly from BMIDA‐terminated alkynes. Besides offering expedient access to seldom studied boryl metal carbenes, these BMIDA gold carbene species undergo facile insertions into methyl, methylene, methine, and benzylic C−H bonds in the absence of the Thorpe–Ingold effect. They also undergo efficient OH insertion, cyclopropanation, and F−C alkylations. This chemistry provides rapid access to structurally diverse α‐BMIDA ketones, which are scarcely documented. In combination with DFT studies, the role of BMIDA is established to be an electron‐donating group that attenuates the high electrophilicity of the gold carbene center. [ABSTRACT FROM AUTHOR]

An Ag/Au‐catalyzed divergent cascade reaction of alkyne embedded diazoketones with indoles has been described. Preliminary mechanistic studies indicate that the reaction goes through a [4+2]‐cycloaddition of an in situ formed isobenzopyrylium intermediate with indole, followed by a sequential retro‐Michael addition/carbene N−H insertion process to give the benzo[i]phenanthridines products with gold catalysis; whereas a dearomatization/rearomatization sequence occurs favourably when the reaction is catalyzed by a silver catalyst, delivering benzo[b]carbazoles in generally high to excellent yields. Notably, this is a rare example of using indole as the dienophile for cycloaddition with the isobenzopyrylium species, providing a concise and practical approach for the selective construction of N‐doped polycyclic aromatic hydrocarbons (PAHs) with structural diversity and broad functional‐group compatibility. [ABSTRACT FROM AUTHOR]

Copper(II) hexafluoroantimonate catalyzes the formal [3 + 3] cycloaddition of Lewis acid activated nitrones and vinyl diazoacetates to produce 1,2-oxazines in high yields and diastereoselectivities. [ABSTRACT FROM AUTHOR]

The reaction is found to result in formation of azabicyclohexanes and/or arylaminofurans depending on the electronic nature of the aryl substituents. [ABSTRACT FROM AUTHOR]

Objective. The objective is to compare the clinical efficacy of laparoscopic resection (LAP), endoscopic full-thickness resection (EFR), and endoscopic submucosal dissection (ESD) in the treatment of gastrointestinal stromal tumors. Methods. The clinical data of 105 patients who were treated in our hospital and diagnosed with GIST by pathology after surgery from March 2019 to March 2021 were collected. Patients were divided into the LAP group, EFR group, and ESD group according to different surgical methods. The clinical data, surgical conditions, complications, and postoperative conditions of the patients were recorded retrospectively. Patients were followed up closely after surgery. Results. The operation time of the EFR group and ESD group was shorter than that of the LAP group, and the operation time of the EFR group was shorter than that of the ESD group (P < 0.05). The amount of intraoperative blood loss in the EFR group and ESD group was lower than that in the LAP group (P < 0.05). There was no significant difference in the complete resection rate among the three groups (P > 0.05). There was no significant difference in the total incidence of complications among the three groups (P > 0.05). The postoperative abdominal pain time, postoperative hospital stay, and total hospitalization costs of the EFR group and ESD group were lower than those of the LAP group (P < 0.05). No recurrence or metastasis cases were found in the three groups during the follow-up period, and there were no GIST-related deaths in the three groups. Conclusion. LAP, EFR, and ESD have good curative effect, good safety, and good prognosis in the treatment of GIST. But compared with LAP, EFR and ESD have the advantages of less trauma, faster recovery, shorter hospitalization time, and lower hospitalization cost. [ABSTRACT FROM AUTHOR]

Background. Realgar was usually selected as a substitute for arsenic trioxide to treat acute promyelocytic leukemia due to its higher effect without high cardiotoxicity. In traditional Chinese medicine (TCM), realgar is usually processed by the water-grinding method clinically, but the mechanism of realgar processing detoxification is still unclear. However, it is necessary to take safety and efficacy into account while evaluating a drug. Methods. Sixty male Wistar rats were divided into control group, realgar products-treated groups, and corresponding subgroups. Biochemistry analysis and histopathological examination were performed in the study, and plasma samples were collected from all the rats for metabolomics analysis. Results. No significant toxicity was observed in rats treated with 0.64 g/kg/day grinding realgar (G-r) and water-grinding realgar (WG-r). When the dose increased to 1.92 g/kg/day, the liver weight coefficients of the rats treated with G-r (HG-r: 3.65 ± 0.26%) and WG-r (HWG-r: 3.67 ± 0.14%) increased significantly and severe hepatic injury occurred in comparison to the control group (Group C: 3.00 ± 0.21%). After one week's withdrawal, the liver injury caused by the high dose of WG-r significantly recovered, while the liver damage caused by G-r was more difficult to recover. In metabolomics analysis, 14 metabolites were identified as the potential biomarkers in realgar-treated rats. These metabolites indicated that there were perturbations of the primary bile acid biosynthesis, arachidonic acid metabolism, linoleic acid metabolism, and glycerophospholipid metabolism in the realgar-treated groups. Conclusions. These results illustrate that, as a TCM processing method, water grinding had the effect of reducing toxicity, and the metabolomics method may be a valuable tool for studying the toxicity induced by TCM and the mechanism of TCM processing. [ABSTRACT FROM AUTHOR]

A mild and facile synthetic method via convergent assembly of two reactive intermediates generated in situ has been developed. This method provides an efficient way to construct six- and seven-membered N -heterocycles containing a biaryl linkage. This reaction features a gem -difunctionalization process of diazo compounds with cyclic hemiaminals, delivering α-hydroxyl-β-amino ester derivatives with a tertiary carbon center through a formal C–O bond-insertion transformation. [ABSTRACT FROM AUTHOR]

An efficient gold and chiral phosphoric acid cooperatively catalyzed enantioselective oxidative cyclization/Mannich-type addition reaction of homopropargyl amides with nitrones has been developed, which provides chiral pyrrolidin-3-ones in high yields with excellent enantioselectivities under mild conditions. This reaction employed stable and readily available alkynes as non-diazo carbene precursors, which provides a 100% atom economy method with high bond formation efficiency. [ABSTRACT FROM AUTHOR]

An enantioselective three-component reaction of vinyl diazosuccinimdes with alcohols and imines has been realized by a cooperative catalysis of Rh2(OAc)4 and a chiral phosphoric acid, leading to chiral 3,3-disubstituted succinimides in good to high yields with high to excellent enantioselectivity. The generated product with an alkenyl species could be converted to the chiral tricyclic structure under mild conditions. [ABSTRACT FROM AUTHOR]

A gold‐catalyzed carbocyclization/C=N bond formation cascade reaction has been developed for the synthesis of polyfunctionalized 4‐iminonaphthalenones and indenes in good to high yields under mild reaction conditions. The reaction goes through 5/6‐endo‐dig diazo‐yne carbocyclization to form the endocyclic vinyl carbene species from corresponding alkyne‐tethered diazo compounds, followed by electrophilic addition/N−O bond cleavage/aromatization sequence with benzo[c]isoxazoles, which features a C=N bond formation process. In addition, the resulting products could be converted into multi‐substituted 2‐naphthol derivatives in high yields. [ABSTRACT FROM AUTHOR]

An unprecedented AgI‐catalyzed efficient method for the coupling of imino ethers and enol diazoacetates through a [3+2]‐cycloaddition/C−O bond cleavage/[1,5]‐proton transfer cascade process is reported. The general class of imino ethers that includes oxazolines, benzoxazoles and benzimidates are applicable substrates for these reactions that provide direct access to fully substituted pyrroles with uniformly high chemo‐ and regioselectivity. High variability in substitution at the pyrrole 2‐, 5‐ and N‐positions characterizes this methodology that also presents an entry point for further pyrrole diversification via facile modification of resulting N‐functional pyrroles. [ABSTRACT FROM AUTHOR]

An unprecedented AgI‐catalyzed efficient method for the coupling of imino ethers and enol diazoacetates through a [3+2]‐cycloaddition/C−O bond cleavage/[1,5]‐proton transfer cascade process is reported. The general class of imino ethers that includes oxazolines, benzoxazoles and benzimidates are applicable substrates for these reactions that provide direct access to fully substituted pyrroles with uniformly high chemo‐ and regioselectivity. High variability in substitution at the pyrrole 2‐, 5‐ and N‐positions characterizes this methodology that also presents an entry point for further pyrrole diversification via facile modification of resulting N‐functional pyrroles. [ABSTRACT FROM AUTHOR]