Palladium-Catalyzed -Selective Arylation of 1-Naphthamide.

Remote C4-H functionalization of -naphthoic acids is highly challenging due to the presence of proximally more accessible C-H bonds at the C2 and C8 positions. Herein, we report the first palladium-catalyzed direct C4 arylation of 1-naphthamides with high regioselectivity and excellent functional group compatibility. Diverse aryl couples were found to be compatible with C4 arylation.

Hydrogen bonding template enables remote meta-C-H alkenylation of nitroarenes with electron-deficient alkenes.

Regioselective distal C-H functionalization of nitroarenes by overriding proximal C-H activation has remained an unsolved challenge. Herein, we present a palladium-catalyzed meta-C-H alkenylation of nitroarene substrate, achieved through leveraging the non-covalent hydrogen bonding interactions. Urea-based templates comprising an elongated biphenyl linker designed in such a way that it interacts with nitro group via strong hydrogen bonding interaction, while a cyano based directing group is attached along the template to coordinate with the palladium center, thereby facilitating the activation of the remote meta-C-H bond of nitrobenzene.

Selective Oxidation of Benzo[]isothiazol-3(2)-Ones Enabled by Selectfluor.

A metal-free and Selectfluor-mediated selective oxidation reaction of benzo[]isothiazol-3(2)-ones in aqueous media is presented. This novel strategy provides a facile, green, and efficient approach to access important benzo[]isothiazol-3(2)-one-1-oxides with excellent yields and high tolerance to various functional groups. Furthermore, the purification of benzoisothiazol-3-one-1-oxides does not rely on column chromatography.

Rh(iii)-catalyzed building up of used heterocyclic cations: facile access to white-light-emitting materials.

The first example of rhodium-catalyzed nondirected C-H activation/annulation reactions for the construction of fused heterocyclic cations is reported herein with excellent regioselectivity. Deuterium-labeling experiments indicated that the C(sp)-H bond cleavage of the -methyl group might be the rate-limiting step during the reaction process. This protocol provides an opportunity to rapidly access highly π-conjugated fused heterocyclic cations, which opens up a new avenue for efficient screening of single-molecular white-light-emitting materials, pure red-light-emitting materials, and π-conjugated radical materials.

Tandem dehydrogenation-olefination-decarboxylation of cycloalkyl carboxylic acids via multifold C-H activation.

Dehydrogenation chemistry has long been established as a fundamental aspect of organic synthesis, commonly encountered in carbonyl compounds. Transition metal catalysis revolutionized it, with strategies like transfer-dehydrogenation, single electron transfer and C-H activation. These approaches, extended to multiple dehydrogenations, can lead to aromatization.

Palladium-Catalyzed -C(sp)-H Bond Arylation of Tertiary Aldehydes Facilitated by 2-Pyridone Ligands.

2-Pyridone ligand-facilitated palladium-catalyzed direct C-H bond functionalization via the transient directing group strategy has become an attractive topic. Here, we report a Pd-catalyzed direct -C(sp)-H arylation reaction of tertiary aliphatic aldehydes by using an -amino acid as a transient directing group in combination with a 2-pyridone ligand.

Disrupting of IGF2BP3-stabilized HK2 mRNA by MYO16-AS1 competitively binding impairs LUAD migration and invasion.

Since invasive cancer is associated with poor clinical outcomes, exploring the molecular mechanism underlying LUAD progression is crucial to improve the prognosis of patients with advanced disease. Herein, we found that MYO16-AS1 is expressed mainly in lung tissue but is notably downregulated in LUAD tissues. Overexpression of MYO16-AS1 inhibited the migration and invasion of LUAD cells.

Combinatorial Ligand Assisted Simultaneous Control of Axial and Central Chirality in Highly Stereoselective C-H Allylation.

The significance of stereoselective C-H bond functionalization thrives on its direct application potential to pharmaceuticals or complex chiral molecule synthesis. Complication arises when there are multiple stereogenic elements such as a center and an axis of chirality to control. Over the years cooperative assistance of multiple chiral ligands has been applied to control only chiral centers.

Access to unsaturated bicyclic lactones by overriding conventional C(sp)-H site selectivity.

Transition metal catalysis plays a pivotal role in transforming unreactive C-H bonds. However, regioselective activation of distal aliphatic C-H bonds poses a tremendous challenge, particularly in the absence of directing templates. Activation of a methylene C-H bond in the presence of methyl C-H is underexplored.

Circular RNA circ-FIRRE interacts with HNRNPC to promote esophageal squamous cell carcinoma progression by stabilizing GLI2 mRNA.

Increasing evidence has shown that circular RNAs (circRNAs) interact with RNA-binding proteins (RBPs) and promote cancer progression. However, the function and mechanism of the circRNA/RBP complex in esophageal squamous cell carcinoma (ESCC) are still largely unknown. Herein, we first characterized a novel oncogenic circRNA, circ-FIRRE, by RNA sequencing (Ribo-free) profiling of ESCC samples.

Photoinduced -Selective C-H Oxygenation of Arenes.

The merger of photocatalysis and transition-metal catalysis has recently emerged as an adaptable platform for the development of innovative and environmentally benign synthetic methodologies. In contrast to classical transformation by Pd complexes, photoredox Pd catalysis operates through a radical pathway in the absence of a radical initiator. Using the synergistic merger of photoredox and Pd catalysis, we have developed a highly efficient, regioselective, and general -oxygenation protocol for diverse arenes under mild reaction conditions.

Site-Selective C-H Functionalization of Carbazoles.

Carbazole alkaloids hold great potential in pharmaceutical and material sciences. However, the current approaches for C1 functionalization of carbazoles rely on the use of a pre-installed directing group, severely limiting their applicability and hindering their overall efficiency. Herein, we report for the first time the development of direct Pd-catalyzed C-H alkylation and acylation of carbazoles assisted by norbornene (NBE) as a transient directing mediator.

Identification of a transcription factor‑cyclin family genes network in lung adenocarcinoma through bioinformatics analysis and validation through RT‑qPCR.

Lung adenocarcinoma (LUAD) is the predominant pathological subtype of lung cancer, which is the most prevalent and lethal malignancy worldwide. Cyclins have been reported to regulate the physiology of various types of tumors by controlling cell cycle progression. However, the key roles and regulatory networks associated with the majority of the cyclin family members in LUAD remain unclear.

Ligand-promoted palladium-catalyzed β-methylene C-H arylation of primary aldehydes.

The transient directing group (TDG) strategy allowed long awaited access to the direct β-C(sp)-H functionalization of unmasked aliphatic aldehydes palladium catalysis. However, the current techniques are restricted to terminal methyl functionalization, limiting their structural scopes and applicability. Herein, we report the development of a direct Pd-catalyzed methylene β-C-H arylation of linear unmasked aldehydes by using 3-amino-3-methylbutanoic acid as a TDG and 2-pyridone as an external ligand.

Palladium-catalyzed direct asymmetric C-H bond functionalization enabled by the directing group strategy.

In the past decade, selective C-C and C-heteroatom bond construction through palladium-catalyzed direct C-H bond functionalization has been extensively studied by employing a variety of directing groups. Within this category, direct asymmetric C(sp)-H and C(sp)-H activation for the construction of highly enantiomerically enriched skeletons still progressed at a slow pace. This minireview briefly introduces the major advances in the field for palladium-catalyzed direct asymmetric C-H bond functionalization the directing group strategy.

Ligand-Enabled δ-C(sp )-H Borylation of Aliphatic Amines.

Directed C-H functionalization has been realized as a complimentary technique to achieve borylation at a distal position of aliphatic amines. Here, we demonstrated the oxidative borylation at the distal δ-position of aliphatic amines using various borylating agents, a palladium catalyst, and a rightly tuned ligand in the presence of a cheap oxidant. Moreover, an organopalladium δ-C(sp )-H-activated intermediate has been isolated and crystallographically characterized to get mechanistic insight.

The mediation effect of maternal glucose on the association between ambient air pollution and birth weight in Foshan, China.

Maternal blood glucose level is associated with fetal growth, therefore, its role in the associations between air pollution and birth weight deserves investigation. We examined the mediation effect of maternal blood glucose on the associations between maternal air pollution exposure and birth weight. A total of 10,904 pregnant women in Foshan, China during 2015-2019 were recruited.

Clinical efficacy of Baihe Gujin decoction combined with anti-tuberculosis therapy for pulmonary tuberculosis with Yin-deficiency and Fire-hyperactivity syndrome.

Objective: To evaluate the clinical efficacy of Baihe Gujin decoction combined with anti-tuberculosis therapy in mitigating the symptoms of pulmonary tuberculosis and to measure the effect on the CD4+ CD25+ regulatory T cell (T) ratio.

Methods: This randomized study enrolled patients with pulmonary tuberculosis and randomly assigned them to one of two treatment groups: an anti-tuberculosis treatment group and a combined treatment group. Bronchoalveolar lavage was performed before and 2 weeks after treatment.

Recent Advances in the Application of Selectfluor as a "Fluorine-free" Functional Reagent in Organic Synthesis.

Selectfluor, [1-chloromethyl-4-fluoro-1,4-diazoniabicyclo-[2.2.2]octane bis(tetrafluoroborate)], is not only an important electrophilic fluorinating agent but also a facile and efficient "fluorine-free" functional reagent in other organic reactions.

Maternal air pollution exposure associated with risk of congenital heart defect in pre-pregnancy overweighted women.

Objectives: Prenatal exposure to air pollutant has been associated with congenital heart defect (CHD). However, no study has investigated this effect in pre-pregnancy overweighted women. This study aimed to evaluate gestational exposure to particulate pollutant (PM) and gaseous air pollutants (O and NO) on the risk of CHD, and explore the potential effect modifiers including maternal age, pre-pregnancy BMI and pregestational diseases.

Lack of association between polymorphism of IL-2 -330T/G and pulmonary tuberculosis among Caucasians.

This meta-analysis was conducted to assess the consistency and strength of the relationship between polymorphism of IL-2 -330T/G and susceptibility to pulmonary tuberculosis (TB). PubMed, Web of Knowledge and CNKI were searched to find eligible studies about the relationship between IL-2 -330T/G polymorphism and susceptibility to pulmonary TB. A total of eight studies comprising 971 cases and 1519 controls were grouped together for the purpose of elucidating the relationship between polymorphism of IL-2 -330T/G and pulmonary TB susceptibility.

Ligand-Controlled Direct γ-C-H Arylation of Aldehydes.

The first example of Pd -catalyzed γ-C(sp )-H functionalization of aliphatic and benzoheteroaryl aldehydes has been developed using a transient ligand and an external ligand, concurrently. A wide array of γ-arylated aldehydes were readily accessed without preinstalling internal directing groups. The catalytic mechanism was studied by performing deuterium-labelling experiments, which indicated that the γ-C(sp )-H bond cleavage is the rate-limiting step during the reaction process.

Silver-Promoted Site-Selective Intramolecular Cyclization of 2-Methylthiobenzamide Through α-C(sp)-H Functionalization.

Silver-mediated intramolecular α-C(sp)-H bond functionalization of the methylthio group has been established in the presence of Selectfluor as an additive. This novel strategy provides efficient access to various diverse sulfur-based heterocycles with good yields and functional group compatibility. It is noteworthy that the completely novel benzooxathiin-4-imine skeletons were reported for the first time in this study.