Palladium-Catalyzed Enantioselective Intramolecular Heck Dearomative Annulation of Indoles with -Tosylhydrazones.

An elegant Pd(dba)-catalyzed enantioselective Heck dearomative annulation of indoles and -tosylhydrazones for the straightforward assembly of structurally diverse optically active indoline scaffolds containing the quaternary carbon centers at the C2 position has been developed. The tandem protocol, which utilized a Pd(dba)/BINOL-based phosphoramidite ligand as the catalytic system, proceeded smoothly through successive oxidative addition, intramolecular carbon palladation, migratory insertion, and β-elimination sequences, leading to the chiral indoline derivatives in moderate to excellent yields, with excellent enantioselectivities and diastereoselectivities. In addition, the synthetic practicability of the catalytic system was underlined by a scaled-up experiment and the late-stage derivatization of the products, thus highlighting the potential applications in synthetic chemistry, medicinal chemistry, and material science.

Lewis Acid Catalyzed [4 + 2] Annulation of Propargylic Alcohols with 2-Vinylanilines.

An elegant Lewis acid catalyzed, protection-free, and straightforward synthetic strategy for the assembly of a series of sophisticated polycyclic quinoline skeletons employing propargylic alcohols and 2-vinylanilines as the substrates in the presence of Yb(OTf) (10 mol %) and AgOTf (10 mol %) in tetrahydrofuran has been described. This annulation protocol, which proceeds through a sequential Meyer-Schuster rearrangement/nucleophilic substitution/deprotonation sequence, provides a versatile, practical, and atom-economical approach for accessing quinoline derivatives in moderate-to-good yields.

New synthetic approaches toward OCF-containing compounds.

Fluorinated organic compounds are an important class of organic molecules and play a key role in both academic and industrial communities due to the unique nature of fluorine. Among the fluorine-containing functional groups, the OCF group is of vital importance because of its favorable physicochemical properties, so it frequently acts as the pivotal skeletal motif in a broad spectrum of pharmaceutical molecules, agrochemicals, natural products, and materials. Over the past few decades, a wider range of strategies for the efficient, versatile, and practical synthesis of trifluoromethoxylated compounds have been the focus of a number of research initiatives.

Palladium-Catalyzed Intramolecular Heck Dearomative Alkenylation of Indoles with -Tosylhydrazones.

An elegant Pd-catalyzed intramolecular Heck dearomative alkenylation of aryl iodides with functionalized -tosylhydrazones proceeded through a sequential dearomative carbopalladation, migratory insertion, and β-hydride elimination in the presence of Pd(CFCOO) (10 mol %), PPh (30 mol %), and CsCO (2.0 equiv) in 1,4-dioxane (2.0 mL) at 120 °C for 14 h under an argon atmosphere.

Visible-Light-Induced Oxyalkylation of 1,2,4-Triazine-3,5(2, 4)-diones with Ethers Oxidative Cross-Dehydrogenative Coupling.

An efficient and convenient method to synthesize 6-oxyalkylated 1,2,4-triazine-3,5(2, 4)-diones has been developed visible-light-induced cross-dehydrogenative coupling reaction between 1,2,4-triazine-3,5(2, 4)-diones and ethers with a wide range of functional group tolerance. The present transformation employs the cheap and low-toxic 2--butylanthraquinone as a metal-free photocatalyst and air as a green oxidant at room temperature. Moreover, this reaction can also be driven by sunlight as a clean energy resource.

Primary Amination of ArP(O)-H with (NH)CO as an Ammonia Source under Simple and Mild Conditions and Its Extension to the Construction of Various P-N or P-O Bonds.

A facile and efficient method for the synthesis of primary phosphinamides from ArP(O)-H reagents with stable and readily available ammonium carbonate as an ammonia source is disclosed herein for the first time. This ethyl bromoacetate-mediated primary amination proceeds smoothly under mild and simple conditions, without any metal catalyst or oxidant. Moreover, this method is also appropriate for the reaction of ArP(O)-H with a variety of amines, alcohols, and phenols to construct P-N or P-O bonds, with features of handy operation, good functional group tolerance, and broad substrate scope.

Palladium-Catalyzed Asymmetric Intramolecular Dearomative Heck Annulation of Aryl Halides to Furnish Indolines.

An unprecedented Pd-catalyzed asymmetric intramolecular cascade cyclization of aryl halides with readily available arylboronic acids proceeds through a Heck-type dearomative cyclization terminated with arylation in the presence of Pd(dba) (10 mol %), CuO (5 mol %), and CsCO (2.0 equiv) in 1,2-dichloroethane (1.0 mL) at 100 °C for 15 h in air using BINOL-based phosphoramidite as the chiral ligand.

Visible-Light-Induced C(sp)-C(sp) Cross-Dehydrogenative-Coupling Reaction of -Heterocycles with -Alkyl--methylanilines under Mild Conditions.

Disclosed herein is a cross-dehydrogenative-coupling reaction of -heterocycles including 1,2,4-triazine-3,5(2, 4)-diones and quinoxaline-2(1)-ones with -methylanilines to form C(sp)-C(sp) under visible-light illumination and ambient air at room temperature. In this process, easily available Ru(bpy)Cl·6HO serves as the catalyst, and air acts as the green oxidant. This method features high atom economy, environmental friendliness, and convenient operation and provides an efficient and practical access to aminomethyl-substituted -heterocycles with extensive functional group compatibility in 40-86% yields.

Direct Introduction of Sulfonamide Groups into Quinoxalin-2(1H)-ones by Cu-Catalyzed C3-H Functionalization.

Direct sulfonamidation of quinoxalin-2(1H)-one derivatives has been developed using a readily available Cu salt as the catalyst and inexpensive ammonium persulfate as the oxidant in moderate conditions. Owing to the feature of handy operation and good functional group tolerance, this method provides a convenient and efficient access to curative 3-sulfonamidated quinoxalin-2(1H)-one scaffolds.

Synthesis of 1,6-Dihydropyridine-3-carbonitrile Derivatives Lewis Acid-Catalyzed Annulation of Propargylic Alcohols with ()-3-Amino-3-phenylacrylonitriles.

A novel Lewis acid-catalyzed, highly efficient, practical, and atom-economical protocol for the synthesis of functionalized 1,2-dihydropyridine-3-carbonitrile derivatives in the presence of Bi(OTf) (10 mol %) in tetrahydrofuran (2.0 mL) at 80 °C for 8 h in air is described, starting from readily accessed propargylic alcohols and ()-3-amino-3-phenylacrylonitriles. This cycloaddition protocol, which is scalable and proceeds under mild conditions, is amenable to the gram-scale construction of valuable 1,2-dihydropyridine-3-carbonitriles.

Silver Trifluoromethanesulfonate-Catalyzed Annulation of Propargylic Alcohols with 3-Methyleneisoindolin-1-one.

A silver-catalyzed formal [3 + 3] annulation of 3-methyleneisoindolin-1-one with alkynol for the synthesis of 1,5-dihydroindolizin-3(2)-one derivatives is disclosed. The protocol allows practical synthesis of -heterocyclic scaffolds with a broad scope of functional groups and could be efficiently scaled up to gram scale, which incarnates a potential application of this methodology. In addition, a range of chlorine anion substitution of alkenes can be constructed by adjusting the structure of the alkynol substrates with the use of TMSCl.

Meteorological factors and water quality changes of Plateau Lake Dianchi in China (1990-2015) and their joint influences on cyanobacterial blooms.

Cyanobacterial blooms (CBs) in eutrophic lakes can cause various harmful issues to both humans and animals, disturb drinking water supply, and devastate lake ecosystems. Although great progresses have been made in many lakes from China and abroad on CBs prevention, mitigation and control, systematic research on the influencing factors of CBs in hypereutrophic plateau Lake Dianchi over a long time span is so far unavailable. This study comprehensively generalized both meteorological and water quality changes in Lake Dianchi during 1990-2015 on both yearly and monthly basis, separated Caohai from Waihai of Lake Dianchi regarding water quality variations, and investigated the individual and joint influencing meteorological and water quality factors on CBs using Spearman correlation, principal component analysis, and multivariate linear stepwise regression.

Base promoted direct difunctionalization/cascade cyclization of 1,6-enynes.

A novel base-mediated direct difluoroalkylation of 1,6-enynes involving a CF2 radical process has been developed. In the absence of metal catalysts, two different difluoroalkylated cyclization products have been synthesized with good functional group applicability and high stereoselectivity. Notably, the properties of a base have been shown to play a crucial role in the generation selectivity of this transformation.

Synthesis of Organophosphorus Compounds through Copper-Catalyzed Annulation Involving C-O and C-P Bond Formations.

A novel copper(II) trifluoromethanesulfonate-catalyzed, high-efficiency, and atom-economical synthesis of valuable organophosphorus compounds via cascade annulation of propargylic alcohols with diphenylphosphine oxide is described. This protocol, which has a good functional-group compatibility and insensitivity to an ambient atmosphere, provides a simple and direct pathway to the products, organophosphorus compounds, in good yields under mild conditions. The method could be efficiently scaled up to gram scale, thus highlighting a potential application of this methodology.

Copper-Catalyzed Oxidative Cyclization of Alkynes with Sulfonylhydrazides Leading to 2-Sulfonated 9H-pyrrolo[1,2-a]indol-9-ones.

A copper-catalyzed oxidative cyclization procedure has been developed for the production of 2-sulfonated 9H-pyrrolo[1,2-a]indol-9-ones via the direct sulfonylation of N-propargyl-substituted indoles with sulfonylhydrazides and tert-butyl hydroperoxide (TBHP). This novel protocol, which tolerates a broad range of functional groups, offers a simple, efficient, and atom-economical route to a series of fluorazones in good yields under mild conditions.

Lewis Acid Catalyzed Dehydrogenative Coupling of Tertiary Propargylic Alcohols with Quinoline N-Oxides.

An unprecedented Lewis acid catalyzed, high-efficiency synthesis of valuable 2-(quinolin-2-yl)prop-2-en-1-ones via dehydrogenative coupling of propargylic alkynols with quinoline N-oxides is described. This protocol, which tolerates a broad range of functional groups, provides a straightforward pathway to the products 2-(quinolin-2-yl)prop-2-en-1-one scaffolds in satisfactory yields. The conversion could be scaled up to gram scale efficiently, which underlines a latent application of this methodology.

[Comparison of Ex Vivo Expanded and Highly Purified NK Cell-Mediated Cytotoxicity Detected by 3 Different Staining Methods of Flow Cytometry].

Objective: To compare the cytotoxicity of ex vivo expanded NK cells detected by flow cytometry with 3 different staining methods.

Methods: NK cells were collected from peripheral blood on the 17 day after culture. The cultured cells were divided into 3 groups: group A , B, and C.

Merging photoredox with copper catalysis: decarboxylative difluoroacetylation of α,β-unsaturated carboxylic acids with ICFCOEt.

A photoredox-/copper-catalyzed decarboxylative difluoroacetylation reaction of α,β-unsaturated carboxylic acids has been developed. This reaction produces a variety of difluoroalkylated alkenes in moderate to excellent yields and exhibits satisfactory stereoselectivity and a broad substrate scope at ambient temperature. Furthermore, this decarboxylative difluoroacetylation protocol provides efficient and environment friendly access to the difluoroalkylated alkenes.

Lewis Acid Catalyzed Cyclization of Propargylic Alcohols with 2-Vinylphenol.

An unprecedented Lewis acid catalyzed, protection-free, and high-efficiency synthesis of valuable 3,4-dihydro-2H-2,4-methanochromans via cycloaddition of propargylic alkynols with 2-vinylphenol is described. This cycloaddition protocol, which tolerates a wide variety of functional groups, provides practical, versatile, and atom-economical access to a new class of appealing bridged-ring products in satisfactory yields. Compared with the reported reaction conditions for bridged-ring skeletons synthesis, the present reaction conditions are neutral, mild, and without any additives.

BF3·OEt2-AgSCF3 Mediated Trifluoromethylthiolation/Cascade Cyclization of Propynols: Synthesis of 4-((Trifluoromethyl)thio)-2H-chromene and 4-((Trifluoromethyl)thio)-1,2-dihydroquinoline Derivatives.

A BF3·OEt2-AgSCF3 mediated direct trifluoromethylthiolation/cascade cyclization of propynols involving the SCF3 anion nucleophilic pathway is developed. This protocol also provides an opportunity to construct valuable trifluoromethylthio-substituted 2H-chromene and 1,2-dihydroquinoline systems with high efficiency under mild conditions. Additionally, the developed BF3·OEt2-AgSCF3 reaction system could be scaled up to gram quantities in a satisfactory yield without inert gas protection.

Lewis Acid Catalyzed [4 + 3] Cycloaddition of Propargylic Alcohols with Azides.

An unprecedented Lewis acid catalyzed [4 + 3] cycloaddition reaction is described that provides a straightforward route to polycyclic products containing an imine-based indole azepine scaffold, starting from readily available internal tertiary alkynols and azides. This cycloaddition protocol provides efficient and atom-economical access to a new class of fascinating imine-containing products in satisfactory yields, which has shown good application in the construction of seven-membered N-heterocycles.

Genetic variations in vitamin D receptor were associated with the outcomes of hepatitis C virus infection among Chinese population.

Vitamin D has been considered as an immune modulator, and exerted the effect through the vitamin D receptor (VDR). This study investigated the associations of single-nucleotide polymorphisms (SNPs) of VDR with the outcomes of Hepatitis C virus (HCV) infection. Three SNPs (rs2228570, rs757343 and rs739837) were genotyped by TaqMan assay among Chinese population, including 538 HCV spontaneous clearance subjects, 834 persistent infection subjects and 1030 uninfected subjects.

Lymphocyte CD64 increased in patients with chronic HBV infection.

CD64 was up-regulated in infection diseases, but there was no report about the change of CD64 in chronic hepatitis B virus (HBV) infection. The purpose of this study was to determine whether there was a dynamic change of CD 64 index and to judge the value to antiviral treatment. 96 CHB patients were enrolled and selected 33 healthy adults as control.

Lewis Acid Mediated Tandem Reaction of Propargylic Alcohols with Hydroxylamine Hydrochloride To Give α,β-Unsaturated Amides and Alkenyl Nitriles.

We have developed a highly selective method for the synthesis of α,β-unsaturated amides and alkenyl nitriles from readily available propargylic alcohols. The reaction proceeded smoothly under the neutral conditions with hydroxylamine hydrochloride (NH2OH·HCl) as the nitrogen source. The development of these new strategies has significantly extended the application of hydroxylamine hydrochloride to the chemistry of propargylic alcohols.

Regulatory T cells and IL-17(+) T helper cells enhanced in patients with chronic hepatitis B virus infection.

Hepatitis B is a worldwide infectious disease caused by hepatitis B virus (HBV), it leaded to millions of deaths every year, HBV mainly through immune response to damage liver cells. The purpose of this study was to judge the value of Regulatory T cells (Treg) and IL-17(+) T helper cells (Th17) in different chronic HBV infection stages. 96 patients with chronic HBV infection were enrolled and selected 33 healthy adults as control.