Fluffy mesoporous AlO supported Ag-InO schottky junction catalysts for selective hydrogenation of CO of α,β-unsaturated aldehydes.

Unsaturated alcohols (UOLs) are important fine chemical intermediates. Thus, it is of great significance to design and prepare catalysts for highly selective hydrogenation of CO of α,β-unsaturated aldehydes (UALs). In this paper, a fluffy mesoporous AlO-supported Ag-InO catalyst (Ag-InO/-AlO) was synthesized by employing a two-solvent method, in which Ag and InO form a Mott-Schottky junction and lead to electron transfer from InO to Ag.

Recent Advances in Nitrene Chemistry with Emerging Precursors.

Nitrene-transfer reaction is one of the powerful synthetic tools in organic chemistry, facilitating a vast array of otherwise unattainable chemical transformations. Different types of nitrene precursors have been exploited and successfully applied in a variety of nitrene-based transformations for the direct construction of nitrogen-containing compounds with structural complexity. Although a few of review articles that focus on the specific nitrene precursors or different type of nitrene reactions have been reported, significant advancements have emerged over the past two decades driven by the introduction and application of novel nitrene precursors, enabling a variety of catalytic transformations for the synthesis of N-heterocyclic frameworks with structural diversity.

IKZF1 promotes pyroptosis and prevents M2 macrophage polarization by inhibiting JAK2/STAT5 pathway in colon cancer.

Pyroptosis and macrophage pro-inflammatory activation play an important role in hepatocellular carcinoma (HCC) progression. However, the specific regulatory mechanisms remain unclear. We identified pyroptosis-related differentially expressed genes (DEGs) based on the GSE4183 and GSE44861 datasets as well as EVenn database.

Revealing the Effects of Mo Doping to Ni on Catalyzing Hydrogenation of Fatty Acids to Fatty Alcohols.

Fatty acid hydrogenation is an important method for the production of fatty alcohols. The combination of Ni and Mo has been reported to be an effective and low-cost catalyst. However, the effect of Mo doping has yet to be fully understood.

Nanoporous High Entropy Alloy Al-Pt-Pd-Ru as an Efficient Catalyst for One-Pot Reductive Amination of Nitroarenes.

High entropy alloys (HEAs) are promising heterocatalysts because of their unique physicochemical properties, but research on HEA-catalyzed tandem reactions is lacking. Moreover, limited research on HEAs for molecular transformation has hindered their development. Herein, an unsupported nanoporous HEA Al-Pt-Pd-Ru (HEANPore) prepared using a top-down dealloying method is reported.

Enantioselective Assembly of Fully Substituted α-Amino Allenoates Through a Mannich Addition and Stepwise [3,3]-σ Rearrangement Sequence.

Chiral fully-substituted allenes are synthetically significant and pivotal building blocks that can engage in diverse transformations toward a variety of bioactive molecules. The enantioselective assembly of these skeletons using readily available reactants offers significant advantages but remains challenging. Herein, an asymmetric formal Michael-type addition of alkynyl imines with the key alkylgold intermediates derived in situ from N-propargylamides is accomplished under gold-complex and chiral quinine-derived squaramide (QN-SQA) synergetic catalysis.

Ternary deep eutectic solvents for esterification of 2-methylpropenoic acid with alcohols.

In this paper, a set of novel ternary deep eutectic solvents (T-DESs) is synthesized and applied in the esterification of 2-methylpropenoic acid with alcohols. T-DESs have multiple functions, serving as a catalyst, polymerization inhibitor, and solvent, and demonstrate excellent catalytic esterification reaction activity (up to 96% yield). The optimal T-DESs 1 can be recycled 14 times without any decrease in its catalytic activity, thus solving the problems of methacrylate product separation with a polymerization inhibitor, catalyst recovery, and organic solvent pollution.

Hydrogenation of CO to formate catalyzed by a Ru catalyst supported on a copolymerized porous organic polymer.

The catalytic hydrogenation of carbon dioxide to formate is of great interest due to its significant role in CO utilization. In this study, a novel heterogeneous Ru(III) catalyst was prepared by immobilizing RuCl on a porous organic polymer (POP) obtained from 1,4-phthalaldehyde (PTA) and 4,4'-biphenyldicarboxaldehyde (BPDA) with melamine. A copolymerization strategy utilizing monomers of varying lengths was employed to prepare the POP-supported Ru catalyst with adjustable porosity.

Palladium-Catalyzed Trifluoroacetylation of Arylboronic Acids Using a Trifluoroacetylation Reagent.

A new trifluoroacetylation reagent was developed by using inexpensive and readily available trifluoroacetic anhydride and -phenyl-4-methylbenzenesulfonamide for the first time. The reaction of (het)aryl boronic acids with the new trifluoroacetylation reagent, -phenyl--tosyltrifluoroacetamide, proceeded smoothly in the presence of a palladium catalyst to provide trifluoromethyl ketones in satisfactory to excellent yields. Various groups, including the synthetically useful functional groups Cl, TMS, and PhCO, were tolerated well under the current reaction conditions.

Photoinduced [4 + 2]-cycloaddition reactions of vinyldiazo compounds for the construction of heterocyclic and bicyclic rings.

Highly selective formal [4 + 2]-cycloaddition of vinyldiazoacetates with azoalkenes from α-halohydrazones, as well as with cyclopentadiene and furan, occurs with light irradiation at room temperature, producing highly functionalized heterocyclic and bicyclic compounds in good yields and excellent diastereoseletivity. Under blue light these vinyldiazoacetate reagents selectively form unstable cyclopropenes that undergo intermolecular cycloaddition reactions at a faster rate than their competitive ene dimerization. [4 + 2]-cycloaddition of vinyldiazoacetates with formed azoalkenes produces bicyclo[4.

A Difluoromethylation Reagent: Access to Difluoromethyl Arenes through Palladium Catalysis.

A new radical difluoromethylation was developed by using inexpensive and readily available difluoroacetic anhydride and -phenyl-4-methylbenzenesulfonamide for the first time. The reaction of arylboronic acids with the new difluoromethylation reagent, -phenyl--tosyldifluoroacetamide, proceeded smoothly in the presence of palladium catalyst to provide difluoromethylarenes in satisfactory to excellent yields. The electronic property (electron-donating or electron-withdrawing) of the substituent linked to the aromatic ring did not considerably influence the reactivity of arylboronic acid.

Contingent magnetic variation and beta-band oscillations in sensorimotor temporal decision-making.

The ability to accurately encode the temporal information of sensory events and hence to make prompt action is fundamental to humans' prompt behavioral decision-making. Here we examined the ability of ensemble coding (averaging multiple inter-intervals in a sound sequence) and subsequent immediate reproduction of target duration at half, equal, or double that of the perceived mean interval in a sensorimotor loop. With magnetoencephalography (MEG), we found that the contingent magnetic variation (CMV) in the central scalp varied as a function of the averaging tasks, with a faster rate for buildup amplitudes and shorter peak latencies in the "half" condition as compared to the "double" condition.

Catalytic [4+2]- and [4+4]-cycloaddition using furan-fused cyclobutanone as a privileged C4 synthon.

Cycloaddition reactions play a pivotal role in synthetic chemistry for the direct assembly of cyclic architectures. However, hurdles remain for extending the C4 synthon to construct diverse heterocycles via programmable [4+n]-cycloaddition. Here we report an atom-economic and modular intermolecular cycloaddition using furan-fused cyclobutanones (FCBs) as a versatile C4 synthon.

Photo-cycloaddition reactions of vinyldiazo compounds.

Heterocyclic rings are important structural scaffolds encountered in both natural and synthetic compounds, and their biological activity often depends on these motifs. They are predominantly accessible via cycloaddition reactions, realized by either thermal, photochemical, or catalytic means. Various starting materials are utilized for this purpose, and, among them, diazo compounds are often encountered, especially vinyldiazo compounds that give access to donor-acceptor cyclopropenes which engage in [2+n] cycloaddition reactions.

HNTf-Catalyzed Formal [3 + 2] Cycloaddition of Vinyldiazoacetates to Indole-Substituted Diazo Compounds and Their Conversion to Carbazoles.

Triflimide catalysis of the [3 + 2]-cycloaddition of 3-indolymethanols with vinyldiazoacetates provides general access to β-tetrahydrocyclopenta[]indol-substituted α-diazoesters. Initiated by addition of the generated vinylogous iminium electrophile from 3-indolymethanol to the vinylogous position of the vinyldiazo compound and completed by intramolecular cyclization from the vinyldiazonium ion intermediate, this transformation occurs in good yields and excellent diastereoselectivity with a broad substrate scope under mild conditions. The resulting α-diazoesters undergo Rh(OAc)-catalyzed substrate-dependent 1,2-migration to form multisubstituted carbazoles in high yields.

Catalytic (4+2) Annulation via Regio- and Enantioselective Interception of in-situ Generated Alkylgold Intermediate.

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.

CHL1 inhibits cell proliferation, migration and invasion by regulating the NF‑κB signaling pathway in colorectal cancer.

Cell adhesion molecule close homolog of L1 (CHL1) is implicated in tumorigenesis of various malignancies. However, its role and underlying molecular mechanisms in colorectal cancer (CRC) remain unclear. The present study aimed to evaluate the specific biological functions and mechanisms of CHL1, in order to provide a theoretical basis for the use of CHL1 as a biological target in CRC.

Visible-Light-Driven Iron-Catalyzed Intermolecular Benzylic C(sp)-H Amination with 1,2,3,4-Tetrazoles.

A visible-light-driven iron-catalyzed C(sp)-H amination of diphenylmethane derivatives with 1,2,3,4-tetrazoles under mild conditions has been developed. The reaction proceeds with photosensitizer-free conditions and features satisfactory to good yields. Mechanistic studies revealed that the reaction proceeded via an iron-nitrene intermediate, and H atom abstraction was the rate-determining step.

Direct synthesis of phenanthrenyl triflates from 1-biphenylyl-2-diazo-2-aryl ketones and triflic anhydride.

A strategy for direct synthesis of phenanthrenyl triflates from 1-biphenylyl-2-diazo-2-aryl ketones and triflic anhydride is described. The reaction of 1-biphenylyl-2-diazo-2-aryl ketones with triflic anhydride proceeded smoothly in the presence of 2,6-di--butylpyridine under mild conditions to produce phenanthrenyl triflates in high to excellent yields. The phenanthrenyl triflate products were demonstrated to be utilized as coupling partners in various coupling reactions.

Visible-Light-Driven Iron-Catalyzed Decarboxylative C-N Coupling Reaction of Alkyl Carboxylic Acids with NaNO.

An efficient visible-light-driven iron-catalyzed decarboxylative C-N coupling reaction of alkyl carboxylic acids with NaNO under mild conditions was developed. The reaction proceeds under photosensitizer-free conditions and features good to excellent yields, broad functional group tolerance, and an easy operation procedure. Preliminary mechanistic investigations showed that visible-light-driven iron catalysis not only achieved oxidative decarboxylation of alkyl carboxylic acids to alkyl radicals but also promoted the reduction of NO to NO, thus leading to the C-N radical coupling reaction.

Cu-catalyzed convenient synthesis of 2-trifluoromethyl benzimidazoles cyclization of -phenylenediamines with hexafluoroacetylacetone.

An efficient and convenient method for the synthesis of 2-trifluoromethyl benzimidazoles is described in this paper. The cyclization reaction of various -phenylenediamines with hexafluoroacetylacetone proceeded smoothly in the presence of CuO as the catalyst to produce 2-trifluoromethyl benzimidazoles in satisfactory to excellent yields (up to >99% yield). The CF source, hexafluoroacetylacetone, acted not only as cyclization partner, but also acted as a ligand for the Cu catalyst.

Modular access to alkylgermanes via reductive germylative alkylation of activated olefins under nickel catalysis.

Carbon-introducing difunctionalization of C-C double bonds enabled by transition-metal catalysis is one of most straightforward and efficient strategies to construct C-C and C-X bonds concurrently from readily available feedstocks towards structurally diverse molecules in one step; however, analogous difunctionalization for introducing germanium group and other functionalities remains elusive. Herein, we describe a nickel-catalyzed germylative alkylation of activated olefins with easily accessible primary, secondary and tertiary alkyl bromides and chlorogermanes as the electrophiles to form C-Ge and C-C bonds simultaneously. This method provides a modular and facile approach for the synthesis of a broad range of alkylgermanes with good functional group compatibility, and can be further applied to the late-stage modification of natural products and pharmaceuticals, as well as ligation of drug fragments.

Visible-light-induced iron-catalyzed reduction of nitroarenes to anilines.

An efficient visible-light-induced iron-catalyzed reduction of nitroarenes to anilines by using -ethylmorpholine (NEM) as a reductant under mild conditions has been developed. The reaction proceeds with photosensitizer-free conditions and features good to excellent yields and broad functional group tolerance. Preliminary mechanistic investigations showed that this reaction was conducted ligand-to-metal (NEM to Fe) charge transfer and nitro triplet biradical-induced hydrogen atom transfer processes.

Base-Catalyzed Nucleophilic Addition Reaction of Indoles with Vinylene Carbonate: An Approach to Synthesize 4-Indolyl-1,3-dioxolanones.

The -functionalized indole is a privileged structural framework in a wide range of bioactive molecules. The nucleophilic addition between indoles with vinylene carbonate proceeded smoothly in the presence of KCO as the catalyst to produce novel indolyl-containing skeletons and 4-indolyl-1,3-dioxolanones in satisfactory to excellent yields (up to >97% yield). Various synthetically useful functional groups, such as halogen atoms, cyano, nitro, and methoxycarbonyl groups, remained intact during the regioselective -H addition reactions.