Enantioselective total syntheses of belactosin A, belactosin C, and its homoanalogue

[reaction: see text] Enantioselective total syntheses of belactosin A, belactosin C, and its homoanalogue have been accomplished in high overall yields (32% for belactosin A from the amino acid 10, and 35 and 36% for belactosin C and its homoanalogue, respectively). This concise approach comprises a novel sequential acylation/beta-lactonization reaction and allows a facile alteration of the substituents, thus providing a flexible route to a new family of highly active belactosin-based proteasome inhibitors.     

Crystal Structures of [Ni(Phen)(i‐Bu2PS2)2] and [Ni(Phen)3](i‐Bu2PS2)2 Complexes and Interaction between Coordinated 1,10‐Phenanthroline Molecules

Single crystals of [Ni(Phen)(iBu₂PS₂)₂] (I) and [Ni(Phen)₃](iBu₂PS₂)₂ (III) compounds were grown, and their structures were determined by Xray diffraction analysis (CAD4 diffractometer, MoK radiation, 3336 F _hkl , R = 0.0373 for I and 2575 F _hkl for III). The crystals of complex I have a triclinic unit cell with the following parameters: a = 11.097(1) , b = 14.903(2) , c = 22.650(3); = 75.18(1)°, = 80.50(1)°, = 75.07(1)°, V = 3479.2(7)³, Z = 4, _calc = 1.255 g/cm³, and space group 1; the crystals of III have a monoclinic unit cell with the following parameters: a = 19.010(3), b = 15.481(1) , c = 17.940(3); = 97.58(1)°, V = 5233.5(12)³, Z = 4, _calc = 1.292 g/cm³, and space group C2/c. The structure of complex I is built from mononuclear molecules, and the structure of III, from [Ni(Phen)₃]²⁺ complex cations and i Bu₂PS₂ ^- outersphere anions. The NiN₂S₄ coordination polyhedra in the structure of I and NiN₆ in the structure of III are distorted octahedra. Based on structural data, the interaction between the coordinated Phen molecules of complexes I, [Ni(Phen)₂(iBu₂PS₂)](iBu₂PS₂) (II), and III is considered, as well as the packing modes of these complexes.     

Synthesis and structure of optically active compounds [Ni(HL1)]NO3 and [Ni(HL2)]NO3H2O containing anions of diaminodioximes H2L1 and H2L2 derived from α-Pinene and (+)-3-Carene as Ligands

New optically active levorotatory compounds [Ni(HL¹)]NO₃ (I) and [Ni(HL²)]NO₃H₂O (II) containing the anions of chiral diaminodioximes, H₂L¹ and H₂L², derived from the terpenes ±-pinene and (+)-3-carene, respectively, were synthesized. Complexes I and II were studied by X-ray diffraction. The crystal structures of compounds are ionic, being composed of the [Ni(HL¹)]⁺ or [Ni(HL²)]⁺ cations and the outer-sphere NO₃^– anions. The Ni²⁺ ion coordinates four N atoms of the tetradentate chelating ligand, the NiN₄ coordination unit being shaped like a tetrahedrally distorted square. Compounds I and II are diamagnetic, which corresponds to a low-spin d⁸ configuration. The NMR spectra of compounds were recorded and analyzed.Translated from Koordinatsionnaya Khimiya, Vol. 30, No. 12, 2004, pp. 888–896.Original Russian Text Copyright © 2004 by Larionov, Myachina, Saveleva, Glinskaya, Klevtsova, Sheludyakova, Tkachev, Bizyaev.     

Volatile coordination compounds of Ni2+ and Co3+ with 1,2-hydroxylaminooximes

Complexes of Ni²⁺ and Co³⁺ with the deprotonated anions of the new ligand N-(3-oximino-2,4-dimethylpentyl-2)hydroxylamine are prepared. The compounds synthesized sublime in vacuum.     

Dimethyl- and Diethyltin(IV) Compounds with Perfluorobiphenyl-4-Thiolate and Perfluoronaphthalene-2-Thiolate Anions: The Crystal Structure of (CH3)2Sn(C12F9S)2

Compounds (CH₃)₂Sn(C₁₂F₉S)₂ (I), (CH₃)₂Sn(C₁₀F₇S)₂ (II), and (C₂H₅)₂Sn(C₁₀F₇S)₂ (III) were synthesized. Single crystals of Iwere grown and structurally characterized using X-ray diffraction analysis (1590 reflections, R = 0.0209). The crystals are orthorhombic, a = 40.848(8) Å, b = 6.058(1) Å, c = 11.183(2) Å, V = 2767(1) ų, (calcd.) = 2.024 g/cm³, space group Pbcn, Z = 4. The structure is built from monomeric molecules. The coordination polyhedron of the Sn atom (the SnC₂S₂ core) is a distorted tetrahedron. Compounds I–III are volatile when heated in vacuo. Thermolysis of these compounds results in SnO₂ (in air) or SnS₂ (in argon).     

Complexes of PdCl2 with chiral oximes of α-(o-anisidino)caranone and α-(o-anisidino)pinanone: synthesis and crystal structures

3-(2-Methoxyphenylamino)caran-4-one and 2-(2-methoxyphenylamino)pinan-3-one E-oximes obtained from appropriate natural terpenes were transformed into 1: 1 complexes with PdCl₂. The structures of the complexes were examined by X-ray diffraction.     

Closed classes containing a homogeneous function class

We consider the structure and basic properties of a superlattice of a class of homogeneous functions of k-valued logic for any k ≥ 2.     

Synthesis and structure of palladium(II) and copper(II) complexes with chiral bis-α-aminooximes containing (+)-3-carene or (+)-limonene fragments and 4,4′-methylenedianiline linker. Crystal structure of the complex [Cu(i-PrOH)Cl2(μ-H2L3)CuCl2·H2O]

Coordination compounds Pd₂(H₂L²)Cl⁴ (I), Cu₂(H₂L²)Cl₄ (II), Pd₂(H₂L³)Cl₄ (III), and Cu₂(H₂L³)Cl₄ (IV), where H₂L² and H₂L³ are chiral bis-α-aminooxime ligands consisting of (+)-3-carene or (+)-limonene fragments and 4,4′-methylenedianiline linker, were synthesized and examined by NMR, ESR, and IR spectroscopy. The structure of [Cu(i-PrOH)CL₂(μ-H₂L³)CuCL₂·H₂O] (V) was determined by X-ray analysis.     

Hydrogen diffusion in steels under electron bombardment

We report on the results of measurement of the coefficients of hydrogen diffusion through metal membranes in the course of their simultaneous hydrogen saturation and bombardment with electrons (energy 30 keV, current density from 3 to 30 µA/cm²) both in a broad and in a narrow beam. It is found that the time of hydrogen discharge from the membrane is determined by the parameters of the electron beam, its periodicity and duration, and also depends on the structure of the phase state of the metal membrane. It is shown that the diffusion coefficient increases when a narrow electron beam in the scanning regime is used. Analysis of the hydrogen yield as a function of time is carried out on a mass spectrometer connected to a vacuum chamber containing an electron gun, a beam sweep oscillator, and an electrolytic cell. The hydrogen diffusion coefficients under the action of a scanning electron beam are 15 times larger than under the same conditions without irradiation.