Reagent‐Based DOS: Developing a Diastereoselective Methodology to Access Spirocyclic‐ and Fused Heterocyclic Ring Systems

Herein, we report a diversity‐oriented‐synthesis (DOS) approach for the synthesis of biologically relevant molecular scaffolds. Our methodology enables the facile synthesis of fused N‐heterocycles, spirooxoindolones, tetrahydroquinolines, and fused N‐heterocycles. The two‐step sequence starts with a chiral‐bicyclic‐lactam‐directed enolate‐addition/substitution step. This step is followed by a ring‐closure onto the built‐in scaffold electrophile, thereby leading to stereoselective carbocycle‐ and spirocycle‐formation. We used in silico tools to calibrate our compounds with respect to chemical diversity and selected drug‐like properties. We evaluated the biological significance of our scaffolds by screening them in two cancer cell‐lines. In summary, our DOS methodology affords new, diverse scaffolds, thereby resulting in compounds that may have significance in medicinal chemistry.     

Cobalt(II)-catalyzed oxidation of alcohols into carboxylic acids and ketones with hydrogen peroxide

The oxidation of aliphatic and aromatic alcohols into the corresponding carboxylic acid analogues and ketones has been carried out using 30% H₂O₂ and cobalt(II) complex 1 in good to high yields. The reaction is safe, clean and functions in the absence of additives.     

Crystal and molecular structure of bis(8-phenylmenthyl) 2-(2-methyl-5-oxo-3-cyclohexen-1-yl)propandioate, C42H54O5· CH3CN

The X-ray crystal structure of the title compound, as crystallized from acetonitrile-water was determined. The relative stereochemistry of the cyclohexenone ring with respect to the 8-phenylmenthyl esters was determined. The title compound crystallizes in the noncentrosymmetric space group P2₁, with a=8.9850(10) ?, b=15.575(3) ?, c=14.478(2) ?, β=94.61(2)°, and D _calc=1.118 g cm⁻³ for Z=2.     

Spin dynamics of layered triangular antiferromagnets with uniaxial anisotropy

The spin dynamics of the semiclassical Heisenberg model with uniaxial anisotropy, on the layered triangular lattice with antiferromagnetic coupling for both intralayer nearest neighbor interaction and interlayer interaction is studied both in the ordered phase and in the paramagnetic phase, using the Monte Carlo-molecular dynamics technique. The important quantities calculated are the full dynamic structure function S(q,ω)$S(\mathbf{q},\omega )$, the chiral dynamic structure function _Schi(ω)$S_{\mathrm{chi}}(\omega )$, the static order parameter and some thermodynamic quantities. Our results show the existence of propagating modes corresponding to both S(q,ω)$S(\mathbf{q},\omega )$ and _Schi(ω)$S_{\mathrm{chi}}(\omega )$ in the ordered phase, supporting the recent conjectures. Our results for the static properties show the magnetic ordering in each layer to be of coplanar 3-sublattice type deviating from 120^°${120}^{°}$ structure. In the presence of magnetic trimerization, however, we find the 3-sublattice structure to be weakened along with the tendency towards non-coplanarity of the spins, supporting the experimental conjecture. Our results for the spin dynamics are in qualitative agreement with those from the inelastic neutron scattering experiments performed recently.     

The radio frequency conductivity of some aliphatic alcohols at different temperatures

Activation energies for viscous flow and conductivity are computed from experimental values of RF conductivity (frequency 400 kHz) at different temperatures for eight polar liquids. It is observed that for aliphatic alcohols the activation energy for conductivity is greater than that for viscous flow. However, their ratio is slightly greater than unity and is different for different alcohols whereas for nonassociating polar liquids the ratio is almost equal to unity. The dependence of conductivity on viscosity for the liquid alcohols does not follow the Walden’s law but can be well represented by Adamczewskis relation.     

Theory of cyclotron resonance halfwidth for electrons scattered by impurities and phonons

A general theory of the cyclotron resonance halfwidth for electrons scattered by impurities and phonons is developed on the basis of the proper connected diagram expansion of the current-correlation-function formula for the dynamic conductivity. The theory is applied to the cases of Ge samples at extremely high magnetic fields and different temperatures. The usual form of Matthiessen's rule Γ = Γ₁ + Γ₂ + …, where Γ and Γ_j are the total and component energy-dependent resonance widths, is valid only if the component widths Γ_j computed separately for each cause of scattering depend linearly on the densities of scatterers. The resonance width Γ_I due to the charged impurities at very low electron densities ($\text{\$}\text{?}$10¹² cm^?3) and at very low temperatures is known to vary in proportion to the square-root of the impurity density. Large deviations from the Matthiessen's rule occur in such a case. The theory is in good quantitative agreement with currently available experimental data. In order to test the generalized form of Matthiessen's rule, however, the high-field resonance experiments around 15 K is desirable where both phonon and impurity scatterings contribute in a comparable manner.     

Some exact solutions in string cosmology

Some Bianchi-type string-cosmological models are presented here. The physical implications of the models are briefly discussed     

Heat transfer by laminar flow of an elastico-viscous liquid along a plane wall with periodic suction

The problem of heat transfer by the laminar flow of an elastico-viscous liquid along a plane wall with periodic suction has been considered. A perturbation technique has been used to obtain an approximate solution of the differential equations. The flow phenomenon has been characterized by the non-dimensional parameters like the elastic number (S), the Reynolds number (R), the Prandtl number (P) and the Eckert number (E). The effects of these parameters on the temperature distributions and the rate of heat transfer at the wall have been studied.     

Preparation,characterization and Mössbauer spectra of the iron(III) complexes of some dihydroxamic acids and amino monohydroxamic acids

Summary Fe^III complexes have been prepared from the dihydroxamic acids (CH₂)_n[CON(R)OH]₂ (n=2, 3, 4, 6, 8; R=H, Ph,o-tolyl,p-tolyl) (H₂L) and the amino monohydroxamic acids H₂NCH(R)CONHOH (R=H, Me) (HL) and XC₆H₄CONHOH (X=o-NH₂,p-NH₂) (HL). Based on elemental analyses, molecular weight data, and electronic and i.r. spectra, the complexes have been formulated as Fe₂(LH)₂L₂, Fe₂L₂O and Fe₂L₃ for the dihydroxamic acids, and Fe(OH)₄L₂(H₂O)₂ and FeL₃ for the amino monohydroxamic acids. The⁵⁷Fe Mossbauer spectra are discussed.The author is née Bose     

The reactivity of methylnickel, -palladium and -platinum compounds towards alkenes and alkynes

The reactivity of alkyl-transition metals towards alkenes and alkynes falls in the sequence Et₂Ni(bipy) > Et₂Pt(bipy) > Me₂Pt(bipy) > MePtCl(bipy) > MePdCl(bipy), which is also the order of decreasing energy of the filled metal d-orbitals.