Diamine bis(phenolate) and pendant amine bis(phenolate) ligands: catalytic activity for the room temperature palladium‐catalyzed Suzuki–Miyaura coupling reaction

A series of amine bis(phenolate) ligands bearing aryl substituents of varying steric bulk are reported and characterized using single‐crystal X‐ray diffraction, NMR spectroscopy and high‐resolution mass spectrometry experiments. Palladium complexes derived in situ from these ligands are evaluated as catalysts for the Suzuki–Miyaura coupling of phenylboronic acid and aryl bromides. High conversions are observed for these reactions in methanol solvent at low catalyst loadings (0.01 mol%), short reaction times (30 min) and mild temperatures (30°C). Conversion is observed for a range of substrates, and is found to depend on the nature of the external base and solvent employed. These findings demonstrate the utility of catalysts derived from late transition metal complexes of amine bis(phenolate) ligands, particularly those bearing bulky cumyl substituents. Copyright © 2015 John Wiley & Sons, Ltd.     

Water-trapping of unstable carbocations taking place into the inverted region of the Marcus equation. First experimental and computational evidence

The reaction rates of the water-trapping of unstable 1-norbornyl cations in relation to the rates of their rearrangement (ring contraction) have been experimentally determined. The activation barrier of the rearrangement reactions was calculated with the QST2 method, whereas the Marcus theory was applied to predict the activation barrier of the trapping reaction. All computations in gas phase were performed with the DFT B3LYP/6-31G(d) method, while the PCM model was used for the computation of unspecific solvent effects. The established methodology was able to predict the major product formed in the solvolysis of the corresponding triflate precursors of the studied carbocations. The agreement between experiment and theory supports, for the first time, the interesting conclusion that the very exergonic trapping-reaction of unstable 1-norbornyl cations takes place with relatively high barriers of activation and, hence, into the Marcus inverted region. Additionally, a noteworthy relationship between the free energy of activation for the carbocation rearrangement in gas phase and the length of the rearranging bond in the ground state is reported.     

Signal processing with multicomponent systems based on metal complexes

Molecular-level systems that respond to external stimulation by changing some physical or chemical properties can be viewed as input–output devices and therefore may be useful for processing information. In recent years, several investigations on species capable of mimicking the function of macroscopic wires, switches, connectors, memories, logic gates, and circuits have been reported. The rational basis for this research stems from the fact that in living organisms information is transported, elaborated and stored by molecular or ionic substrates operating in a solution-based environment. Because of their diverse and valuable physico-chemical properties, metal complexes have been extensively used as functional components for the construction of artificial molecular devices capable of processing information. Here we illustrate recent progress, and discuss limitations and perspectives of this research area.     

Asymmetric synthesis of 4-ethoxy-1-p-tolylsulfonyl-3,6-dioxabicyclo[3.1.0]hexan-2-ones

Optically pure sulfinylfuranones undergo oxidation at sulfur followed by a totally stereoselective epoxidation at the electron deficient double bond by treatment with MCPBA at room temperature to afford, in good yields, enantiomerically pure 4-ethoxy-5-alkyl-1-p-tolylsulfonyl-3,6-dioxabicyclo[3.1.0]hexan-2-ones. These epoxyfuranones are obtained along with cyclopropanefuranones by reaction of 4-ethoxy-6-p-tolylsulfinylfuro[3,4-c]pyrazolin-6-ones with MPCBA. In both cases, the formation of the sulfonyl epoxylactones takes place by oxidation of the sulfonylfuran-2(5H)-one resulting from the starting materials. This reaction is completely stereoselective (controlled by the configuration of C-5 of furanone) and results from the nucleophilic attack of the peroxycarboxylate generated by interaction of the reagent with weak basic centres at the substrates.     

Surface characteristics of activated carbons obtained by pyrolysis of plasma pretreated PET

Activated carbon materials have been prepared by pyrolysis of plasma pretreated recycled PET. The obtained carbon materials have been texturally characterized by N2 (77 K) and CO2 (273 K) adsorption. Atomic force microscopy (AFM) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) have been used to analyze the surface of the treated precursors. Carbon materials obtained by He, N2, and CO2 plasma pretreatments (4 min) of the precursor and subsequent pyrolysis have shown a higher adsorption capacity than the corresponding chars (untreated pyrolised PET). This effect seems to be related to the elimination by the plasma treatments of low-molecular-weight products in the precursor, which are responsible for the formation of amorphous carbon deposits during the carbonization that blocks the porosity. Longer periods of treatment (15 min) do not favor the opening of the microporosity because cross-linking reactions in the precursor producing high molecular weight deposits prevail. The development of porosity is less relevant if oxygen plasma is used, as a considerable amount of oxygen functionalities are also formed. These groups can decompose during pyrolysation producing the above-mentioned amorphous carbon deposits. The textural characteristics of the carbon materials obtained after 4 min of plasma treatment on the precursor are very similar to those obtained after 4 h of CO2 (1073 K) activation of the same char. Therefore, this method can be an alternative to avoid the burnoff and high energy cost of the activation step.     

Linear programming with fuzzy parameters: An interactive method resolution

This paper proposes a method for solving linear programming problems where all the coefficients are, in general, fuzzy numbers. We use a fuzzy ranking method to rank the fuzzy objective values and to deal with the inequality relation on constraints. It allows us to work with the concept of feasibility degree. The bigger the feasibility degree is, the worst the objective value will be. We offer the decision-maker (DM) the optimal solution for several different degrees of feasibility. With this information the DM is able to establish a fuzzy goal. We build a fuzzy subset in the decision space whose membership function represents the balance between feasibility degree of constraints and satisfaction degree of the goal. A reasonable solution is the one that has the biggest membership degree to this fuzzy subset. Finally, to illustrate our method, we solve a numerical example.     

Inhibitory G proteins and their receptors: emerging therapeutic targets for obesity and diabetes

The worldwide prevalence of obesity is steadily increasing, nearly doubling between 1980 and 2008. Obesity is often associated with insulin resistance, a major risk factor for type 2 diabetes mellitus (T2DM): a costly chronic disease and serious public health problem. The underlying cause of T2DM is a failure of the beta cells of the pancreas to continue to produce enough insulin to counteract insulin resistance. Most current T2DM therapeutics do not prevent continued loss of insulin secretion capacity, and those that do have the potential to preserve beta cell mass and function are not effective in all patients. Therefore, developing new methods for preventing and treating obesity and T2DM is very timely and of great significance. There is now considerable literature demonstrating a link between inhibitory guanine nucleotide-binding protein (G protein) and G protein-coupled receptor (GPCR) signaling in insulin-responsive tissues and the pathogenesis of obesity and T2DM. These studies are suggesting new and emerging therapeutic targets for these conditions. In this review, we will discuss inhibitory G proteins and GPCRs that have primary actions in the beta cell and other peripheral sites as therapeutic targets for obesity and T2DM, improving satiety, insulin resistance and/or beta cell biology.     

In situ formation and reaction of 2-pyridylboronic esters

2-Pyridylboronic esters were generated by cross-coupling 2-bromopyridines with bis(pinacolato)diboron in the presence of a base and palladium catalyst. The boronic esters reacted in situ with unreacted 2-bromopyridines to afford high yields of 2,2′-bipyridines as homocoupled products. Depending upon the reaction conditions, varying amounts of protodeboronated products were also observed. An attempted cross-coupling between two different 2-bromopyridines produced a nearly statistical mixture of homo- and cross-coupled products.