Ring expansion of indene by photoredox-enabled functionalized carbon-atom insertion.

Skeletal editing has received unprecedented attention as an emerging technology for the late-stage manipulation of molecular scaffolds. The direct achievement of functionalized carbon-atom insertion in aromatic rings is challenging. Despite ring-expanding carbon-atom insertion reactions, such as the Ciamician-Dennstedt re-arrangement, being performed for more than 140 years, only a few relevant examples of such transformations have been reported, with these limited to the installation of halogen, ester and phenyl groups.

Essential blood molecular signature for progression of sepsis-induced acute lung injury: Integrated bioinformatic, single-cell RNA Seq and machine learning analysis.

In this study, we aimed to identify an essential blood molecular signature for chacterizing the progression of sepsis-induced acute lung injury using integrated bioinformatic and machine learning analysis. The results showed that a total of 88 functionally related ALI-associated hub genes in sepsis were identified by MCODE analysis and they were enriched in infection and inflammtory responses, lung and cardiovascular disease pathways. These hub genes stratified ALI-sepsis and sepsis and further stratified two subtypes of sepsis-ALI with differential ALI scores, hub gene expression patterns, and levels of immune cells.

Magnetic Excitations in Ferromagnetically Coupled Spin-1 Nanographenes.

In the pursuit of high-spin building blocks for the formation of covalently bonded 1D or 2D materials with controlled magnetic interactions, -electron magnetism offers an ideal framework to engineer ferromagnetic interactions between nanographenes. As a first step in this direction, we explore the spin properties of ferromagnetically coupled triangulenes-triangular nanographenes with spin . By combining in-solution synthesis of rationally designed molecular precursors with on-surface synthesis, we successfully achieve covalently bonded triangulene dimers and trimers on Au(111).

Nitrogen-to-functionalized carbon atom transmutation of pyridine.

The targeted and selective replacement of a single atom in an aromatic system represents a powerful strategy for the rapid interconversion of molecular scaffolds. Herein, we report a pyridine-to-benzene transformation nitrogen-to-carbon skeletal editing. This approach proceeds a sequence of pyridine ring-opening, imine hydrolysis, olefination, electrocyclization, and aromatization to achieve the desired transmutation.

Tosylazide as N1-Synthon: Iron-Catalyzed Nitrogenative Dimerization of Indoles to -Bisindolopyrazine Derivatives.

We present a straightforward one-step process to access a range of novel -diindolepyrazines via an unprecedented [-BuN][Fe(CO)(NO)] (TBA[Fe])-catalyzed intermolecular nitrogenative dimerization of various indole derivatives. Remarkably, tosylazide functions as a N1-synthon forming the central pyrazine unit that joins the two indole subunits. The catalytic transformation shows a good substrate scope, and the obtained products show interesting electronic properties.

Modular Synthesis of Structurally Diverse Azulene-Embedded Polycyclic Aromatic Hydrocarbons by Knoevenagel-Type Condensation.

The research interest in azulene-embedded polycyclic aromatic hydrocarbons (PAHs) has significantly increased recently, but the lack of efficient synthetic strategies impedes the investigation of their structure-property relationships and further opto-electronic applications. Here we report a modular synthetic strategy towards diverse azulene-embedded PAHs by a tandem Suzuki coupling and base-promoted Knoevenagel-type condensation with good yields and great structural versatility, including non-alternant thiophene-rich PAHs, butterfly- or Z-shaped PAHs bearing two azulene units, and the first example of a two-azulene-embedded double [5]helicene. The structural topology, aromaticity and photophysical properties were investigated by NMR, X-ray crystallography analysis and UV/Vis absorption spectroscopy assisted by DFT calculations.

Copper-catalyzed defluorinative arylboration of vinylarenes with polyfluoroarenes.

An unprecedented but challenging defluorinative arylboration has been achieved. Enabled by a copper catalyst, an interesting procedure on defluorinative arylboration of styrenes has been established. With polyfluoroarenes as the substrates, this methodology offers flexible and facile access to provide a diverse assortment of products under mild reaction conditions.

Matrine suppresses NLRP3 inflammasome activation via regulating PTPN2/JNK/SREBP2 pathway in sepsis.

Background: Sepsis is defined as life-threatening organ dysfunction caused by a dysregulated host response to infection. Abnormal activation of NOD-like receptor thermal protein domain associated protein 3 (NLRP3) inflammasome plays a vital role in the pathogenesis of sepsis. Matrine is proved to show good anti-inflammatory properties, whereas its effect and the underlying molecular machinery on sepsis remains unclear.

Copper-Catalyzed Boroaminomethylation of Olefins to γ-Boryl Amines with CO as C1 Source.

Boroaminomethylation of olefins is an efficient process to convert hydrocarbons directly into boron-, nitrogen-containing molecules. Such chemicals are a good handle for obtaining more complexed amine derivatives through the various transformations of organoboron. However, using simple and easily available CO as the C1 feedstock to achieve boroaminomethylation is still elusive.

Catalyst-controlled selective borocarbonylation of benzylidenecyclopropanes: regiodivergent synthesis of γ-vinylboryl ketones and β-cyclopropylboryl ketones.

Regioselective catalytic multi-functionalization reactions enable the rapid synthesis of complexed products from the same precursors. In this communication, we present a method for the regiodivergent borocarbonylation of benzylidenecyclopropanes with aryl iodides. Various γ-vinylboryl ketones and β-cyclopropylboryl ketones were produced in moderate to good yields with excellent regioselectivity from the same substrates.

Copper-catalyzed borofunctionalization of styrenes with Bpin and CO.

The construction of structurally complexed and high-value chemical molecules from simple and readily available feedstocks is a long-standing challenge to chemists. Here, we describe a copper-catalyzed borofunctionalization of styrenes with Bpin and carbon monoxide. A set of new sodium cyclic borates were obtained with NaO Bu as the base.

Observation of fractional edge excitations in nanographene spin chains.

Fractionalization is a phenomenon in which strong interactions in a quantum system drive the emergence of excitations with quantum numbers that are absent in the building blocks. Outstanding examples are excitations with charge e/3 in the fractional quantum Hall effect, solitons in one-dimensional conducting polymers and Majorana states in topological superconductors. Fractionalization is also predicted to manifest itself in low-dimensional quantum magnets, such as one-dimensional antiferromagnetic S = 1 chains.

Copper-Catalyzed 1,2-Trifluoromethylation Carbonylation of Unactivated Alkenes: Efficient Access to β-Trifluoromethylated Aliphatic Carboxylic Acid Derivatives.

A novel copper-catalyzed carbonylative trifluoromethylation of unactivated alkenes has been developed. A broad range of β-trifluoromethylated carboxylic acid derivatives were prepared in moderate to excellent yields from simple alkenes with excellent regioselectivity. It is noteworthy that ethylene gas, as the simplest olefin, can also be applied directly to obtain β-trifluoromethylated amides and ester.

Pd/Cu-Catalyzed amide-enabled selectivity-reversed borocarbonylation of unactivated alkenes.

The addition reaction between CuBpin and alkenes to give a terminal boron substituted intermediate is usually fast and facile. In this communication, a selectivity-reversed procedure has been designed and established. This selectivity-reversed borocarbonylation reaction is enabled by a cooperative action between palladium and copper catalysts and proceeds with complete regioselectivity.

Copper-Catalyzed Borylative Methylation of Alkyl Iodides with CO as the C1 Source: Advantaged by Faster Reaction of CuH over CuBpin.

CuH and CuBpin are versatile catalysts and intermediates in organic chemistry. However, studies that involve both CuH and CuBpin in the same reaction is still rarely reported due to their high reactivity. Now, a study on CuH- and CuBpin-catalyzed borylative methylation of alkyl iodides with CO as the C1 source is reported.

Pd/Cu-Catalyzed Defluorinative Carbonylative Coupling of Aryl Iodides and gem-Difluoroalkenes: Efficient Synthesis of α-Fluorochalcones.

An unprecedented and challenging defluorinative carbonylation was achieved. Enabled by a Pd/Cu cooperative catalyst system, the first example of defluorinative carbonylative coupling has been established. With gem-difluoroalkenes and aryl iodides as the substrates, this methodology offers flexible and facile access to privileged α-fluorochalcones under mild reaction conditions in moderate-to-excellent yields.

Ligand-Controlled Copper-Catalyzed Regiodivergent Carbonylative Synthesis of α-Amino Ketones and α-Boryl Amides from Imines and Alkyl Iodides.

Regioselective transformation is among the long-standing challenges in organic synthesis. In this communication, a copper-catalyzed selectivity controlled regiodivergent borocarbonylation of imines with alkyl iodides has been developed. Various α-amino ketones and α-boryl amides were produced in moderate to good yields from the same substrates.

Copper-Catalyzed Carbonylative Hydroamidation of Styrenes to Branched Amides.

Amides are one of the most ubiquitous functional groups in synthetic and medicinal chemistry. Novel and rapid synthesis of amides remains in high demand. In this communication, a general and efficient procedure for branch-selective hydroamidation of vinylarenes with hydroxyamine derivatives enabled by copper catalysis has been developed for the first time.

Copper-Catalyzed Synthesis of Stereodefined Cyclopropyl Bis(boronates) from Alkenes with CO as the C1 Source.

A novel copper-catalyzed stereodefined procedure for the selective synthesis of cyclopropyl bis(boronates) from terminal alkenes has been developed. Various aliphatic alkenes were transformed into the desired bis(boronate ester)-substituted cyclopropanes in moderate to good yields. Synthetic transformations of the resulting cyclopropyl bis(boronates) demonstrate their utility.

Four-Component Borocarbonylation of Vinylarenes Enabled by Cooperative Cu/Pd Catalysis: Access to β-Boryl Ketones and β-Boryl Vinyl Esters.

We report here a general four-component synthetic procedure for the preparation of β-boryl ketones and β-boryl vinyl esters. Joint catalyzed by palladium and copper catalysts, borocarbonylative reaction between vinylarenes, aryl halides/triflates, B Pin , and carbon monoxide proceed successfully. A variety of synthetically useful β-boryl ketones were synthesized in good to high yields by using aryl iodides as the substrates.

Copper-Catalyzed Regioselective Borocarbonylative Coupling of Unactivated Alkenes with Alkyl Halides: Synthesis of β-Boryl Ketones.

The borocarbonylative coupling of unactivated alkenes with alkyl halides remains a challenge. In this communication, a Cu-catalyzed borocarbonylative coupling of unactivated alkenes with alkyl halides for the synthesis of β-boryl ketones has been developed. A broad range of β-boryl ketone derivatives was prepared in moderate to excellent yields with complete regioselectivity.

Short-Axis Methyl Substitution Approach on Indacenodithiophene: A New Multi-Fused Ladder-Type Arene for Organic Solar Cells.

Indacenodithiophene (IDT) is a promising building block for designing organic semiconductors. In this work, a new pentacyclic ladder-type arene IDMe was designed and synthesized by introducing methyl substitution on the short-axis of IDT. Two non-fullerene electron acceptors (IDIC and ID-MeIC) without and with methyl substitution were designed and synthesized for further study.