Visible Light-Induced Carbonylation Reactions with Organic Dyes as the Photosensitizers.

Dyes can CO do it: Organic dyes and pigments are usually applied in textile dyeing, which can be dated back to the Neolithic period. Interestingly, the possibility to use organic dyes as photoredox catalysts has also been noticed by organic chemists and applied in organic synthesis. Carbonylation reactions as a powerful procedure in carbonyl-containing compound preparation have also been studied.

A general iodine-mediated synthesis of primary sulfonamides from thiols and aqueous ammonia.

A general and efficient methodology for preparing primary sulfonamides has been developed. In the presence of iodine as the catalyst and TBHP (70% in water) as the oxidant, a wide range of primary sulfonamides were prepared from the corresponding thiols and aqueous ammonia in moderate to good yields.

Copper-Catalyzed Carbonylative Coupling of Cycloalkanes and Amides.

Carbonylation reactions are a most powerful method for the synthesis of carbonyl-containing compounds. However, most known carbonylation procedures still require noble-metal catalysts and the use of activated compounds and good nucleophiles as substrates. Herein, we developed a copper-catalyzed carbonylative transformation of cycloalkanes and amides.

Palladium-Catalyzed Construction of Amidines from Arylboronic Acids under Oxidative Conditions.

A valuable palladium-catalyzed three-component coupling reaction for the synthesis of amidines has been developed. Using arylboronic acids, isocyanides, and anilines as the reactants under oxidative conditions, various amidines were isolated in good yields with good functional group tolerances.

Palladium-Catalyzed Carbonylative Four-Component Synthesis of Thiochromenones: The Advantages of a Reagent Capsule.

Multicomponent reactions, especially those involving four or even more reagents, have been a long-standing challenge because of the issues associated with balancing reactivity, selectivity, and compatibility. Herein, we demonstrate how the use of a reagent capsule provides straightforward access to synthetically valuable thiochromenone derivatives by a palladium-catalyzed carbonylative four-component reaction. To the best of our knowledge, this is the first example of applying a capsule to prevent catalyst poisoning and undesired side reactions of the multicomponent reaction.

Comparison of the values of MRI diffusion kurtosis imaging and diffusion tensor imaging in cerebral astrocytoma grading and their association with aquaporin-4.

Objective: To compare the value of MRI diffusion kurtosis imaging (DKI) and diffusion tensor imaging (DTI) in grading cerebral astrocytomas and to analyze the correlation of respective parameters with aquaporin-4 (AQP4) expression.

Methods: Sixty patients with cerebral astrocytoma, including low-grade astrocytomas (LGA, n = 25) and high-grade astrocytomas (HGA, n = 35), were studied. The values of DKI parameters (mean kurtosis [MK], radial kurtosis [Kr], and axial kurtosis [Ka]) and DTI parameters (fractional anisotropy, mean diffusivity [MD]) corrected by contralateral normal-appearing white matter in the solid parts of the tumors and peritumoral edema were compared.

A Convenient Palladium-Catalyzed Reductive Carbonylation of Aryl Iodides with Dual Role of Formic Acid.

Palladium-catalyzed reductive carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source.

A Lysosome-Targeting Fluorescence Off-On Probe for Imaging of Nitroreductase and Hypoxia in Live Cells.

A lysosome-targeting fluorescent off-on probe has been developed by one-step synthesis for detecting lysosomal nitroreductase and hypoxia. The probe is constructed by incorporating morpholine (a lysosome-targeting unit) into 4-nitro-1,8-naphthalimide (as a fluorochrome and specific substrate for nitroreductase), and the detection mechanism is based on the nitroreductase-catalyzed reduction of the probe to 4-amino-1,8-naphthalimide, accompanied by a large fluorescence enhancement at a wavelength of 543 nm. The probe shows an accurate lysosome-targeting ability with high selectivity and sensitivity to nitroreductase (detection limit: 2.

[Application of Micro-aerobic Hydrolysis Acidification in the Pretreatment of Petrochemical Wastewater].

Micro-aerobic hydrolysis acidification technology was applied in the reconstruction of ananaerobic hydrolysis acidification tank in a north petrochemical wastewater treatment plant. After put into operation, the monitoring results showed that the average removal rate of COD was 11.7% when influent COD was 490.

[Pharmacokinetics and MR imaging of SPIO-shRNA dual functional molecular probe in vivo].

In this study, we investigated the pharmacokinetics parameters of SPIO-shRNA dual functional molecular probe and observed the main organ distribution by MRI in vivo. Eighteen New Zealand white rabbits were randomly divided into three groups and injected intravenously with different doses of SPIO-shRNA molecular probe, respectively. The blood samples were collected to analyze the pharmacokinetic parameters by measuring the iron content at 30 minutes before and after the injection.

N-methyl-D-aspartic acid receptor 1 (NMDAR1) aggravates secondary inflammatory damage induced by hemin-NLRP3 pathway after intracerebral hemorrhage.

Objective: Inflammation plays a critical role in secondary brain damage after intracerebral hemorrhage (ICH). However, the mechanisms of inflammatory injury following ICH are still unclear, particularly the involvement of NLRP3 inflammasome, which are crucial to sterile inflammatory responses. In this study, we aim to test the hypothesis that NLRP3 signaling pathway takes a vital position in ICH-induced secondary inflammatory damage and detect the role of N-methyl-D-aspartic acid receptor 1 (NMDAR1) in this progress.

Transition Metal-free Methylation of Amines with Formaldehyde as the Reductant and Methyl Source.

A simple transition metal-free procedure using formal dehyde for the N,N-dimethylation and N-methylation of primary and secondary anilines is reported. The reaction showed limitations on sterically hindered and electron-withdrawing anilines, but is successful on amines with electron-donating substituents. Formaldehyde acts as both the reducing agent and the carbon source in the reaction.

A Convenient Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Halides with Formic Acid as the Carbon Monoxide Source.

A practical palladium-catalyzed carbonylative Suzuki coupling of aryl halides under carbon monoxide gas-free conditions has been developed. Here, formic acid was utilized as the carbon monoxide source for the first time with acetic anhydride as the additive. A variety of diarylketones were produced in moderate to excellent yields from the corresponding aryl halides and arylboronic acids.

Differentiation of high-grade-astrocytomas from solitary-brain-metastases: Comparing diffusion kurtosis imaging and diffusion tensor imaging.

Objective: To compare the value of MRI diffusion kurtosis imaging (DKI) and diffusion tensor imaging (DTI) in differentiating high-grade-astrocytomas from solitary-brain-metastases.

Methods: Thirty-one high-grade-astrocytomas and twenty solitary-brain-metastases were retrospectively identified. DKI parameters [mean kurtosis (MK), radial kurtosis (Kr), and axial kurtosis (Ka)] and DTI parameters [fractional anisotropy (FA) and mean diffusivity (MD)] values with and without correction by contralateral normal-appearing white matter (NAWM) in the tumoral solid part and peritumoral edema, were compared using the t-test.

[Optimal concentration of superparamagnetic iron oxide-short hairpin RNA dual functional molecular probe transfected into ovarian cancer cells in vitro].

Objective: To explore the effects of superparamagnetic iron oxide-short hairpin RNA (SPIO-ShRNA) dual functional molecular probes of different concentrations on morphology and biological behavior of ovarian cancer SKOV3 cells in vitro.

Methods: The dual functional molecular probes at an iron concentration of 5, 15, 30, 45, 75, and 100 mg/L were transfected into SKOV3 cells. The transfection rate of the probe was observed by fluorescence microscope.

Palladium-Catalyzed Carbonylative Cyclization of Arenes by C-H Bond Activation with DMF as the Carbonyl Source.

A novel palladium-catalyzed CO-gas- and autoclave-free protocol for the synthesis of 11H-pyrido[2,1-b]quinazolin-11-ones has been developed. Quinazolinones, which are omnipresent motif in many pharmaceuticals and agrochemicals, were prepared in good yields by C-H bond activation and annulation using DMF as the CO surrogate. A (13) CO-labelled DMF control experiment demonstrated that CO gas was released from the carbonyl of DMF with acid as the promotor.

Toward Greener Oxidative Transformations: Base-Metal Catalysts and Metal-Free Reactions.

In this account, the advances in base-metal-catalyzed oxidative transformations and metal-free oxidation reactions developed in our group are summarized and discussed. Related achievements from other research groups are also discussed.

Synthesis of quinazolinimines and quinazolinamines from 2-fluorobenzonitriles under catalyst-free conditions.

A convenient procedure for the synthesis of quinazolinimines and quinazolinamines from 2-fluorobenzonitriles has been developed. By using KO(t)Bu as the promotor with 2-aminopyridines or amidines as the reaction partner, the desired heterocycles were produced in moderate to good yields under catalyst-free conditions.

A Practical and General Base-Catalyzed Carbonylation of Amines for the Synthesis of N-Formamides.

A highly practical and general base-catalyzed carbonylation of amines to the corresponding N-formamides has been realized. Cheap inorganic bases, including Group IA and IIA metal hydroxides, alkoxides, carbonates, and phosphates, were effective catalysts for the transformation. In the presence of 10-40 mol % of KOH or K2 CO3 , various amines were converted into the corresponding N-formamides in good-to-excellent yields using CO as the formylation reagents.

Acylation of (Hetero)Arenes through C-H Activation with Aroyl Surrogates.

In this Minireview, the major achievements in the acylation of arenes and heteroarenes by C-H activation with aroyl groups are summarized and discussed. As the products are carbonyl-containing compounds that are typical products from carbonylation chemistry, the possible inspirations for these reactions are also discussed, as are mechanistic issues and possible problems for carbonylative diaryl ketone synthesis by C-H activation.

Palladium-Catalyzed One-Pot Carbonylative Sonogashira Reaction Employing Formic acid as the CO Source.

A convenient palladium-catalyzed carbonylative coupling of aryl iodides and terminal alkynes with formic acid as the CO precursor has been developed. A variety of alkynones were obtained in good yields in a one-pot manner for the first time.

Palladium-catalyzed carbonylative Sonogashira coupling between aryl triazenes and alkynes.

We developed a palladium-catalyzed carbonylative Sonogashira reaction with aryl triazenes and alkynes as substrates and methanesulfonic acid as the additive. A series of α,β-ynones were synthesized by this alternative procedure. Notably, bromides, iodides and hydroxyl groups could be well-tolerated under these reaction conditions.

N2 extrusion and CO insertion: a novel palladium-catalyzed carbonylative transformation of aryltriazenes.

A novel procedure for the replacement of N2 with CO of aryltriazenes has been developed. Aryltriazenes were converted to the corresponding arylamides catalyzed by 1 mol % of PdCl2/P(o-Tol)3 under CO pressure. In this process, aryldiazonium salts were generated in the presence of 40 mol % of MeSO3H.

Palladium-catalyzed aminocarbonylation of N-chloroamines with boronic acids.

Aryl (pseudo)halide-based (C-X) carbonylation reactions have been extensively studied during the past few decades. From both academic and synthetic points of view, the carbonylative transformation of N-X bonds represents an interesting and attractive area of investigation. In light of this, the first carbonylative cross-coupling between N-chloroamines and organoboronic acids has been developed.