6-Bromoindole- and 6-Bromoindazole-Based Inhibitors of Bacterial Cystathionine γ-Lyase Containing 3-Aminothiophene-2-Carboxylate Moiety.

In recent years, a number of synthetic potentiators of antibiotics have been discovered. Their action can significantly enhance the antibacterial effect and limit the spread of antibiotic resistance through inhibition of bacterial cystathionine-γ-lyase. To expand the known set of potentiators, we developed methods for the synthesis of five new representatives of 6-bromoindole derivatives-potential inhibitors of bacterial cystathionine-γ-lyase-namely potassium 3-amino-5-((6-bromoindolyl)methyl)thiophene-2-carboxylate () and its 6-bromoindazole analogs ( and ), along with two 6-broindazole analogs of the parent compound .

The concept of Gallium-controlled double C-H functionalization of aliphatic CH-groups driven by Vinyl carbocations.

The direct C-H activation of inert C(sp)-H bonds in a hydrocarbon chain has been a very attractive target in organic synthesis for many decades. Among all the variety of processes, those driven by vinyl carbocations are quite scarce thus far, and it is hard to control for unstabilized vinyl cations. In this study, we designed a double C(sp)-H functionalization of unactivated alkyl CH groups to produce a totally substituted quaternary carbon stereocenter via insertion of vinyl carbocations.

Left Ventricular Diastolic Dysfunction in Cardiac Surgery: A Narrative Review.

Cardiac relaxation is a complex process that involves various interconnected characteristics and, along with contractile properties, determines stroke volume. Perioperative ischemia-reperfusion injury and left ventricular diastolic dysfunction (DD) are characterized by the left ventricle's inability to receive a sufficient blood volume under adequate preload. Baseline DD and perioperative DD have an impact on postoperative complications, length of hospital stay, and major clinical outcomes in a variety of cardiac pathologies.

Boronyl Borinic Esters: Preparation as B pin / BuLi/TFAA Adducts, Structural Insights and Reactivity in Pd-catalyzed Allylic Borylation.

Novel boronyl borinic ester I was generated by quenching the B pin / BuLi-ate complex with trifluoroacetic acid anhydride (TFAA) via ring-opening in the 1,3,2-dioxaborolane moiety on ate-boron. Detailed NMR studies of the B pin / BuLi-ate complex in solution and in solid state allowed us to assume its oligomeric nature in solids with only ate-boron involved in the oligomerization process. The O-trifluoroacetyl pinacolate residue on borinic ester I initially formed on quenching with TFAA undergoes an unusual intramolecular transesterification with the carbonyl group of trifluoroacetyl forming othroester moiety in a few hours at r.

Synthesis of the Indole-Based Inhibitors of Bacterial Cystathionine γ-Lyase NL1-NL3.

Bacterial cystathionine γ-lyase (bCSE) is the main producer of HS in pathogenic bacteria such as , , etc. The suppression of bCSE activity considerably enhances the sensitivity of bacteria to antibiotics. Convenient methods for the efficient synthesis of gram quantities of two selective indole-based bCSE inhibitors, namely (2-(6-bromo-1-indol-1-yl)acetyl)glycine (NL1), 5-((6-bromo-1-indol-1-yl)methyl)- 2-methylfuran-3-carboxylic acid (NL2), as well as a synthetic method for preparation 3-((6-(7-chlorobenzo[]thiophen-2-yl)-1-indol-1-yl)methyl)- 1-pyrazole-5-carboxylic acid (NL3), have been developed.

A Versatile Equilibrium Method for the Synthesis of High-Strength, Ladder-like Polyphenylsilsesquioxanes with Finely Tunable Molecular Parameters.

A versatile equilibrium method for synthesizing ladder-like polyphenylsilsesquioxanes (L-PPSQs) with various molecular weights (from 4 to 500 kDa) in liquid ammonia was developed. The effect of diverse parameters, such as temperature, monomer concentration, reaction time, addition or removal of water from the reaction medium, on the polycondensation process was determined. The molecular weight characteristics and structure of the L-PPSQ elements obtained were determined by GPC, H, Si NMR, IR spectroscopy, viscometry, and PXRD methods.

(2-Fluoroallyl)pyridinium tetrafluoroborates: novel fluorinated electrophiles for Pd-catalyzed allylic substitution.

An efficient two-step approach to 2-fluoroallyl amines was developed that involves the synthesis of (2-fluoroallyl)pyridinium tetrafluoroborates from readily available gem-bromofluorocyclopropanes and the application of the former as novel and stable 2-fluoroallyl electrophiles for Pd-catalyzed allylic substitution.

(2-Fluoroallyl)boration of Ketones with (2-Fluoroallyl)boronates.

Efficient routes toward activation of -chlorofluorocyclopropane-derived (2-fluoroallyl)boronates for allylboration of various ketones including functionalized and low-reactive ones were developed. Increasing the boron electrophilicity by the transformation of a boronate moiety into a borinic ester with BuLi/trifluoroacetic anhydride (TFAA) makes (2-fluoroallyl)boration of acetyl arenes/hetarenes and aliphatic ketones possible with high diastereoselectivity. For low-reactive or sterically hindered ketones (e.

A Systematic Review and International Web-Based Survey of Randomized Controlled Trials in the Perioperative and Critical Care Setting: Interventions Increasing Mortality.

Objective: Reducing mortality is a key target in critical care and perioperative medicine. The authors aimed to identify all nonsurgical interventions (drugs, techniques, strategies) shown by randomized trials to increase mortality in these clinical settings.

Design: A systematic review of the literature followed by a consensus-based voting process.

A Systematic Review and International Web-Based Survey of Randomized Controlled Trials in the Perioperative and Critical Care Setting: Interventions Reducing Mortality.

The authors aimed to identify interventions documented by randomized controlled trials (RCTs) that reduce mortality in adult critically ill and perioperative patients, followed by a survey of clinicians' opinions and routine practices to understand the clinicians' response to such evidence. The authors performed a comprehensive literature review to identify all topics reported to reduce mortality in perioperative and critical care settings according to at least 2 RCTs or to a multicenter RCT or to a single-center RCT plus guidelines. The authors generated position statements that were voted on online by physicians worldwide for agreement, use, and willingness to include in international guidelines.

(2-Fluoroallyl)boronates: new reagents for diastereoselective 2-fluoroallylboration of aldehydes.

A Pd-catalyzed borylation of 2-fluoroallyl chlorides with B2pin2 in the presence of [(2-MeAll)PdCl]2/TMEDA or [(2-MeAll)Pd(IPr)Cl] was developed to afford (2-fluoroallyl)pinacolboronates with high Z-selectivity. The products proved to be useful for anti-selective 2-fluoroallylboration of aromatic and aliphatic aldehydes.

Phosphocreatine in Cardiac Surgery Patients: A Meta-Analysis of Randomized Controlled Trials.

Objective: There is experimental evidence that phosphocreatine (PCr) can decrease ischemia/reperfusion injury of the heart. The authors investigated if PCr would improve heart performance as compared with standard treatment in cardiac surgery.

Design: Meta-analysis of randomized controlled trials.

Trifluoromethylation of aryl and heteroaryl halides with fluoroform-derived CuCF3: scope, limitations, and mechanistic features.

Fluoroform-derived CuCF3 recently discovered in our group exhibits remarkably high reactivity toward aryl and heteroaryl halides, performing best in the absence of extra ligands. A broad variety of iodoarenes undergo smooth trifluoromethylation with the "ligandless" CuCF3 at 23-50 °C to give the corresponding benzotrifluorides in nearly quantitative yield. A number of much less reactive aromatic bromides also have been trifluoromethylated, including pyridine, pyrimidine, pyrazine, and thiazole derivatives as well as aryl bromides bearing electron-withdrawing groups and/or ortho substituents.

Oxidative stress and liver monooxygenase function after heart valve surgery.

Background And Objectives: this prospective study was carried out to evaluate oxidative stress and liver monooxygenase function after cardiac surgery in patients with acquired valvular heart disease.

Methods: 97 patients were studied. Oxidative stress was quantified with malondialdehyde, coupled trienes, hepatocuprein, and catalase activity.

Direct cupration of fluoroform.

We have found the first reaction of direct cupration of fluoroform, the most attractive CF(3) source for the introduction of the trifluoromethyl group into organic molecules. Treatment of CuX (X = Cl, Br, I) with 2 equiv of MOR (M = K, Na) in DMF or NMP produces novel alkoxycuprates that readily react with CF(3)H at room temperature and atmospheric pressure to give CuCF(3) derivatives. The CuCl and t-BuOK (1:2) combination provides best results, furnishing the CuCF(3) product within seconds in nearly quantitative yield.