Benzylation of nitroalkanes using copper-catalyzed thermal redox catalysis: toward the facile C-alkylation of nitroalkanes

The C-alkylation of nitroalkanes under mild conditions has been a significant challenge in organic synthesis for more than a century. Herein we report a simple Cu(I) catalyst, generated in situ, that is highly effective for C-benzylation of nitroalkanes using abundant benzyl bromides and related heteroaromatic compounds. This process, which we believe proceeds via a thermal redox mechanism, allows access to a variety of complex nitroalkanes under mild reaction conditions and represents the first step toward the development of a general catalytic system for the alkylation of nitroalkanes.     

Dimethylamine borane dehydrogenation chemistry: syntheses, X-ray and neutron diffraction studies of 18-electron aminoborane and 14-electron aminoboryl complexes

The reactions of Me(2)NH·BH(3) with cationic Rh(III) and Ir(III) complexes have been shown to generate the 18-electron aminoborane adduct [Ir(IMes)(2)(H)(2){κ(2)-H(2)BNMe(2))](+) and the remarkable 14-electron aminoboryl complex [Rh(IMes)(2)(H)-{B(H)NMe(2))](+). Neutron diffraction studies have been used for the first time to define H-atom locations in metal complexes of this type formed under catalytic conditions.     

A tandem oximation-cyclization route to Δ-isoxazolines

3,5-Disubstituted Δ²-isoxazolines can be prepared from the corresponding β,γ-unsaturated ketones by treatment with hydroxylamine hydrochloride and sodium hydroxide. Evidence indicates that the mechanism of this reaction involves the formation of three intermediates; oximation of the ketone, rearrangement of the alkene, and intramolecular Michael addition of the resulting α,β-unsaturated oxime.     

Azomethine ylides from tin-substituted cyclic carbinol amides: a new route to highly substituted pyrrolizidines

[reaction: see text] Addition of organolithium and organomagnesium reagents to N-(tri-n-butylstannylmethyl)phthalimides yields N-(tri-n-butylstannylmethyl) cyclic carbinol amides, which form azomethine ylides upon treatment with HF.pyridine. This novel route to azomethine ylides allows rapid access to highly functionalized pyrrolizidines (1,2,3,9b-tetrahydropyrrolo[2,1-a]isoindol-5-ones).     

Computational engineering to enhance the photovoltaic by end-capped and bridging core alterations: Empowering the future with solar energy through synergistic effect in D-A materials

Organic photovoltaic solar cells are being designed to offer a low energy photovoltaic (PV) solution. Optimizing the molecular backbone is one the most important technique for improving the photovoltaic characteristic of A-D-A type small active layer molecules. Herein, we have designed and theoretical characterized six new molecules by end-capped and bridging core modifications of recently synthesized molecule BFHIC-4F. Enhancement in photovoltaic, optoelectronic and physio-chemical properties of newly designed molecules are seen by doing such modifications. Different advanced quantum chemical techniques have been employed to evaluate the performance of newly planned molecules. Large open circuit voltage and narrow band gap suggested that the designed molecules are efficient aspirants for solar cell applications. Moreover, maximum absorption capability in near-infra-red (NIR) region is observed for these newly designed molecules. To sum up, outcomes of all analyses advocated that the designed molecules are efficient candidates for solar cell applications.     

Encapsulation of cyclodextrin complexed simvastatin in chitosan nanocarriers: A novel technique for oral delivery

The purpose of the present work was to design and investigate the potential of novel hydroxylpropyl-beta-cyclodextrin (HP-β-CD) and chitosan nanocarriers (NCs) for effective delivery of model, poorly water soluble drug simvastatin. The prepared system was characterized for particle size, particle size distribution (PDI), zeta potential, differential scanning calorimetery, x-ray diffraction, encapsulation efficiency and drug release studies. The results revealed that among the selected ratios of tripolyphosphate/chitosan, ratio 1:4 and 1:5 proved to be optimum in terms of particle size, particle distribution and drug release profile. The average size of nanoparticles increased from 516 to 617 and 464 to 562 nm for ratio 1:4 and 1:5 with increase in drug/HP-β-CD amount. To assess interactions and whether the simvastatin was incorporated in the NCs in its crystalline or amorphous form DSC and XRD were performed. These results suggest that the encapsulation process produces a marked decrease in crystallinity of simvastatin and/or confers to a nearly amorphous state of drug in NCs. Results reveled that with increase in the amount of HP-β-CD/drug the final loading of the NCs increased due to increased solubilization of simvastatin in the presence of HP-β-CD. The in vitro release profile of prepared NCs showed initial fast release (burst effect) followed by a delayed release pattern. In conclusion, these nanocarriers constitute a novel and efficient system for encapsulation and oral delivery of poorly soluble drugs.     

Anilide activation of adjacent C-H bonds in the palladium-catalysed Fujiwara-Moritani reaction

The Pd(II)-catalysed oxidative counterpart of the Heck reaction, originally described by Fujiwara and Moritani, has been studied in detail by a combination of NMR, single-crystal X-ray diffraction and substrate variation. The process involves a palladacycle that is a true intermediate in catalysis. Pd(OAc)(2) is first converted into a more electrophilic palladium species for effective catalysis, defining the main role of added acid. In the course of these studies, three palladacyclic intermediates have been characterised by X-ray diffraction, firstly the directly produced acetate complex 1, the camphorsulfonate complex 2, and additionally tosylate 3, isolated from a reacting system, demonstrating the accessibility of a cationic or comparably electrophilic palladium entity under turnover conditions. The isolated palladacycle 3 is also an effective catalyst. The reaction rate shows a first-order dependency on [anilide] and [Pd], but not on benzoquinone, alkene or p-TsOH. Acid, in the form of p-TsOH, is an essential component, whereas acetate is dispensable. A crossover experiment involving distinct substitution in reactant and palladacycle demonstrates that the palladacycle is directly involved in the catalysis.     

High‐Purity Discrete PEG‐Oligomer Crystals Allow Structural Insight

To great (monodisperse) lengths : An improved synthesis of purer ethylene glycol (EG) oligomers allows access to 16‐ and 32‐mers pure enough for multiple incorporation, and also to the longest (48‐mer) discrete EG oligomer yet reported. The high purity enables the first crystallizations and hence the first glimpses of secondary 3₁₀‐helical PEG structures.