Carbonylative Suzuki coupling reactions catalyzed by ONO pincer–type Pd(II) complexes using chloroform as a carbon monoxide surrogate

Benzoylhydrazone Schiff base–ligated three new ONO pincer–type palladium(II) complexes, [(PdL¹(PPh₃)] ( 1 ), [(PdL²(PPh₃)] ( 2 ), and [(PdL³(PPh₃)] ( 3 ), were synthesized by the reaction of the respective ligand, N-(2-hydroxybenzylidene)benzohydrazide (HL¹), N-(2-hydroxy-3-methoxybenzylidene)benzohydrazide (HL²), or N-(5-bromo-2-hydroxybenzylidene) benzohydrazide (HL³), with Pd(OAc)₂ and PPh₃ in methanol and isolated as air-stable reddish-orange crystalline solids in high yields (78%–83%). All three complexes were fully characterized by elemental analysis, Fourier-transform infrared spectroscopy, UV–Visible, ¹H nuclear magnetic resonance (NMR), ¹³C{¹H} NMR, and ³¹P{¹H} NMR spectroscopic studies. The molecular structure of all three complexes was established unambiguously by single-crystal X-ray diffraction studies which revealed a distorted square planar geometry of all three complexes. The ONO pincer–type ligands occupied three coordination sites at the palladium, while the fourth site is occupied by the monodentate triphenylphosphine ligand. The catalytic potential of all three complexes was explored in the carbonylative Suzuki coupling of aryl bromides and iodides with arylboronic acids to yield biaryl ketones, using CHCl₃ as the source of carbonyl. The reported protocol is convenient and safe as it obviates the use of carbon monoxide (CO) balloons or pressured CO reactors which are otherwise needed for the carbonylation reactions. The methodology has been successfully applied to the synthesis of two antineoplastic drugs, namely, phenstatin and naphthylphenstatin, in good yields (81% and 85%, respectively). Under the optimized reaction conditions, complex 2 exhibited the best catalytic activity in the carbonylative Suzuki couplings. The reported catalysts have wide reaction scope with good functional group tolerance. All catalysts could be retrieved from the reaction after completion and recycled up to three times with insignificant loss in the catalytic activity.     

Synthesis of anomerically pure vinyl sulfone-modified pent-2-enofuranosides and hex-2-enopyranosides: a group of highly reactive Michael acceptors for accessing carbohydrate based synthons

Syntheses of the benzyl or the trityl protected α- and β-anomers of vinyl sulfone-modified pent-2-enofuranosides have been initiated by the ring opening of the suitably masked methyl α-lyxofuranosyl-epoxide or methyl β-ribofuranosyl-epoxide or by the nucleophilic displacement of the leaving groups in benzyl protected 3-O-tosyl xylofuranoside and 3-O-mesyl ribofuranoside by p-thiocresol. In case of the latter set of starting materials, α- and β-methyl glycosides formed in almost equal ratio only from the derivatives of d-xylose. For the synthesis of α- and β-anomers of vinyl sulfone-modified hex-2-enopyranosides, a d-glucose derivative was selected over a d-allose derivative as the starting material because the former almost exclusively produced the required methyl pyranosides whereas the latter produced a mixture. All sulfides were converted to vinyl sulfone-modified carbohydrates by the sequential application of oxidation, mesylation and base induced elimination reactions.     

Self-energy of a charge near a metal surface

A quantum mechanical expression for the self-energy of a charged particle near a metal surface has been derived. The expression incorporates the interaction of the charge with the surface and bulk plasmons including their dispersions in the hydrodynamic model. It is found that the inclusion of the plasmons dispersions gives result for the saturated value of the image potential for copper closer to experiment.     

Synthesis,microstructure, and copolymerization studies of 2-chloroethyl α-chloroacrylate

Poly(2-chloroethyl α-chloroacrylate) was synthesized by radical initiation, and its microstructure was evaluated using carbon-13 NMR. Methyl methacrylate (M₁) and 2-chloroethyl α-chloroacrylate (M₂) were copolymerized in toluene at 55°C using azobisisobutyronitrile as initiator. The reactivity ratios are 0.37 ± 0.28 and 1.21 ± 2.26, The thermal properties of these copolymers have also been reported.     

Continuous and discrete Bessel wavelet transforms

Using the theory of Hankel convolution, continuous and discrete Bessel wavelet transforms are defined. Certain boundedness results and inversion formula for the continuous Bessel wavelet transform are obtained. Important properties of the discrete Bessel wavelet transform are given.     

Biosynthesis of silver nanoparticles using <Emphasis Type="Italic">Carissa carandas</Emphasis> berries and its potential antibacterial activities

Metal nanoparticles synthesis using the biological material offers a simple, biocompatible, cost-effective and nontoxic in character. A number of plant materials have been utilized as resource material for the most favorable biosynthesis of active nanomaterials. This study involves the synthesis of active silver nanoparticles (Ag NPs) using the Carissa carandas (Karonda) berry water extract at room temperature. The nanoparticles characterized at several parameters including shape, size, mass and charge with help of electron microscopy (TEM), Fourier transforms IR (FTIR), UV-VIS spectroscopy and Raman spectroscopy which proved the efficient silver nanoparticles to be useful in several practical applications. The UV-visible spectra showed the surface plasmon resonance peak at ~440?nm, which is weel recognized attribute peak in case of silver nanoparticles. Avarage size of the biogenic silver nanoparticles ranged from ~10–60?nm, predominantly spherical in shape. The suggested possible mechanisms for the synthesis of silver nanoparticles relies on reduction of AgNO₃ due to occurrence of carinol (and related resonant compounds) in the berry extract with inductive effect of the proton of methoxy and allyl groups, present at ortho and para positions of the compounds. The biologically synthesized Ag NPs also showed efficient antibacterial activity against different pathogenic and non-pathogenic bacteria at par with the generic antibiotics.

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Synthesis of combinatorial libraries based on terpenoid scaffolds

Triterpenoid-based scaffolds betulinic acid (1a) and ursolic acid (1b), have been used for the generation of combinatorial libraries in parallel format using solid phase organic synthesis method. These templates have the potential for the synthesis and amplification of triterpenoid-based compounds with one and two-point diversity. This has been demonstrated by the synthesis of two small libraries comprising 18 derivatives each of betulinic acid and ursolic acid with structural diversity at C-3 and C-28 positions. The primary screening of antimalarial activity of these libraries against P. falciparum in vitro led to the identification of four compounds with 5 fold increase in the activity compared to betulinic and ursolic acids.