One-Pot Multicomponent Reactions for the Efficient Synthesis of Highly Functionalized Dihydropyridines

Abstract

An efficient, atom-economic, one-pot protocol has been developed for the synthesis of highly functionalized dihydropyridines via four-component reactions of aromatic aldehydes, arylamines, malononitrile, and dimethylacetylenedicarboxylate in the presence of sodium hydroxide in ethanol. This domino reaction proceeded smoothly in good to excellent yields and offered several advantages, including short reaction time, simple experimental procedure, and applicability to a broad range of substrates.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

N‐Heterocyclic Carbene,High Oxidation State Molybdenum Alkylidene Complexes: Functional‐Group‐Tolerant Cationic Metathesis Catalysts

We synthesized the first N‐heterocyclic carbene (NHC) complexes of Schrock’s molybdenum imido alkylidene bis(triflate) complexes. Unlike existing bis(triflate) complexes, the novel 16‐electron complexes represent metathesis active, functional‐group‐tolerant catalysts. Single‐crystal X‐ray structures of two representatives of this novel class of Schrock catalysts are presented and reactivity is discussed in view of their structural peculiarities. In the presence of monomer (substrate), these catalysts form cationic species and can be employed in ring‐closing metathesis (RCM), ring‐opening metathesis polymerization (ROMP), as well as in the cyclopolymerization of α,ω‐diynes. Monomers containing functional groups, which are not tolerated by the existing variations of Schrock’s catalyst, e.g., sec‐amine, hydroxy, and carboxylic acid moieties, can be used. These catalysts therefore hold great promise in both organic and polymer chemistry, where they allow for the use of protic monomers.     

Heterometallic Triply‐Bridging Bis‐Borylene Complexes

Triply‐bridging bis‐{hydrido(borylene)} and bis‐borylene species of groups 6, 8 and 9 transition metals are reported. Mild thermolysis of [Fe₂(CO)₉] with an in situ produced intermediate, generated from the low‐temperature reaction of [Cp*WCl₄] (Cp*=η⁵‐C₅Me₅) and [LiBH₄?THF] afforded triply‐bridging bis‐{hydrido(borylene)}, [(μ₃‐BH)₂H₂{Cp*W(CO)₂}₂{Fe(CO)₂}] ( 1 ) and bis‐borylene, [(μ₃‐BH)₂{Cp*W(CO)₂}₂{Fe(CO)₃}] ( 2 ). The chemical bonding analyses of 1 show that the B?H interactions in bis‐{hydrido (borylene)} species is stronger as compared to the M?H ones. Frontier molecular orbital analysis shows a significantly larger energy gap between the HOMO‐LUMO for 2 as compared to 1 . In an attempt to synthesize the ruthenium analogue of 1 , a similar reaction has been performed with [Ru₃(CO)₁₂]. Although we failed to get the bis‐{hydrido(borylene)} species, the reaction afforded triply‐bridging bis‐borylene species [(μ₃‐BH)₂{WCp*(CO)₂}₂{Ru(CO)₃}] ( 2′ ), an analogue of 2 . In search for the isolation of bridging bis‐borylene species of Rh, we have treated [Co₂(CO)₈] with nido‐[(RhCp*)₂(B₃H₇)], which afforded triply‐bridging bis‐borylene species [(μ₃‐BH)₂(RhCp*)₂Co₂(CO)₄(μ‐CO)] ( 3 ). All the compounds have been characterized by means of single‐crystal X‐ray diffraction study; ¹H, ¹¹B, ¹³C NMR spectroscopy; IR spectroscopy and mass spectrometry.     

Effect of heat treatment on the physico-chemical properties and catalytic activity of manganese nodules leached residue towards decomposition of hydrogen peroxide

The effect of calcination temperature on the physico-chemical characterization of manganese nodule leached residue (MNLR) and water-washed manganese nodule leached residue (WMNLR) has been investigated on the basis of chemical analysis, XRD, TG-DTA, FTIR, surface hydroxyl groups, surface oxygen, reducing and oxidizing sites, surface area. XRD and IR confirm the presence of amorphous iron oxyhydroxides, delta-MnO2, which are converted to alpha-Fe2O3 and gamma-Mn2O3 phases above 400 degrees C of calcination, respectively. A solid solution of Fe2O3 and Mn2O3 is formed above 700 degrees C. The surface area, surface hydroxyl group, surface oxygen, reducing and oxidizing sites increase with the increase in calcination temperature up to 400 degrees C and then decrease with further rise in calcination temperature up to 700 degrees C. The catalytic activity of the sample towards H2O2 decomposition shows the similar trend as surface properties. A suitable Mn(3+)Mn4+ couple favours H2O2 decomposition reaction. The activity has been correlated with various physico-chemical properties.     

Synthesis,Spectroscopic Studies,and Biological Activity of Organosilicon(iv) Complexes of Ligands Derived from 2-Aminobenzothiazole Derivatives and 2-Hydroxy-3-Methoxy Benzaldehyde

Abstract

The Schiff bases derived from the condensation of 2-aminobenzothiazole derivatives and 2-hydroxy-3-methoxybenzaldehyde and their silicon(IV) complexes with the general formula R₂Si(L)Cl (R = Et, Bu, Ph, L = 2-(2-hydroxy-3-methoxy) benzylideneaminobenzo-thiazole) have been synthesized. These complexes have been characterized by elemental analysis, molar conductance, and spectroscopic studies including IR and NMR (¹H, ¹³C, and ²⁹Si) spectroscopy. The analytical data suggest trigonal bipyramidal geometry around the silicon atom in the resulting complexes. The ligands and their organosilicon complexes have also been evaluated for in vitro antimicrobial activity against bacteria (Staphylococcus aureus, Bacillus subtilis, and Escherichia coli) and fungi (Aspergillus niger and Candida albicans). The complexes were found to be more potent as compared to the ligands.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

GPU‐accelerated direct numerical simulations of decaying compressible turbulence employing a GKM‐based solver

Gas Kinetic Method‐based flow solvers have become popular in recent years owing to their robustness in simulating high Mach number compressible flows. We evaluate the performance of the newly developed analytical gas kinetic method (AGKM) by Xuan et al. in performing direct numerical simulation of canonical compressible turbulent flow on graphical processing unit (GPU)s. We find that for a range of turbulent Mach numbers, AGKM results shows excellent agreement with high order accurate results obtained with traditional Navier–Stokes solvers in terms of key turbulence statistics. Further, AGKM is found to be more efficient as compared with the traditional gas kinetic method for GPU implementation. We present a brief overview of the optimizations performed on NVIDIA K20 GPU and show that GPU optimizations boost the speedup up‐to 40x as compared with single core CPU computations. Hence, AGKM can be used as an efficient method for performing fast and accurate direct numerical simulations of compressible turbulent flows on simple GPU‐based workstations. Copyright © 2016 John Wiley & Sons, Ltd.     

Mechanical loads on a generalized thermoelastic medium with diffusion

The disturbance caused by the application of continuous mechanical source on the free surface of a homogeneous, isotropic elastic half space in the context of the theory of generalized thermoelastic diffusion with one relaxation time parameter is investigated in the Laplace-Fourier transform domain for a two dimensional problem using eigenvalue approach. The integral transforms are inverted by using a numerical technique. The expressions for displacement components, stresses, temperature field, concentration and chemical potential so obtained in the physical domain are computed numerically and illustrated graphically at different times, for copper like material. As a special case the effect of diffusion on various expressions has also been obtained analytically and depicted graphically.