Hydrogenation of schiff bases with group 6 metal carbonyls and sodium methoxide as catalyst precursors

Summary Schiff bases are hydrogenated to secondary amines by H₂ in the presence of [M(CO)₆](M=Cr, Mo or W) and NaOMe in methanol solution at 60–160 °C andca. 100 bar H₂ pressure. The reaction is significantly slower in the absence of NaOMe. In a stoichiometric reaction, [HCr(CO)₅]^– hydrogenatesN- benzylidene-aniline at 75 °C toN-benzylaniline forming [Cr₂(CO)₁₀]^2–.     

Catalytic non-conventional trans-hydroboration: a theoretical and experimental perspective

We have studied the non-conventional trans-hydroboration reaction of alkynes both experimentally and theoretically. A catalytic system based on the in situ mixture of [{Rh(cod)Cl}(2)]/PCy(3) (cod=1,5-cyclooctadiene, Cy=cyclohexyl) has been able to activate pinacolborane and catecholborane and transfer boryl and hydride groups onto the same unhindered carbon atom of the terminal alkynes. The presence of a base (Et(3)N) favored the non-conventional trans-hydroboration over the traditional cis-hydroboration. Varying the substrate had a significant influence on the reaction, with up to 99% conversion and 94% regioselectivity observed for para-methyl-phenylacetylene. Both DFT and quantum mechanical/molecular mechanical ONIOM calculations were carried out on the [RhCl(PR(3))(2)] system. To explain the selectivity towards the (Z)-alkenylboronate we explored several alternative mechanisms to the traditional cis-hydroboration, using propyne as a model alkyne. The proposed mechanism can be divided into four stages: 1) isomerization of the alkyne into the vinylidene, 2) oxidative addition of the borane reagent, 3) vinylidene insertion into the Rh-H bond, and finally 4) reductive elimination of the C-B bond to yield the 1-alkenylboronate. Calculations indicated that the vinylidene insertion is the selectivity-determining step. This result was consistent with the observed Z selectivity when the sterically demanding phosphine groups, such as PCy(3) and PiPr(3), were introduced. Finally, we theoretically analyzed the effect of the substrate on the selectivity; we identified several factors that contribute to the preference for aryl alkynes over aliphatic alkynes for the Z isomer. The intrinsic electronic properties of aryl substituents favored the Z-pathway over the E-pathway, and the aryl groups containing electron donating substituents favored the occurrence of the vinylidene reaction channel.     

The metal loading ability of beta-amyloid N-terminus: a combined potentiometric and spectroscopic study of copper(II) complexes with beta-amyloid(1-16), its short or mutated peptide fragments, and its polyethylene glycol (PEG)-ylated analogue

Alzheimer's disease (AD) is becoming a rapidly growing health problem, as it is one of the main causes of dementia in the elderly. Interestingly, copper(II) (together with zinc and iron) ions are accumulated in amyloid deposits, suggesting that metal binding to Abeta could be involved in AD pathogenesis. In Abeta, the metal binding is believed to occur within the N-terminal region encompassing the amino acid residues 1-16. In this work, potentiometric, spectroscopic (UV-vis, circular dichroism, and electron paramagnetic resonance), and electrospray ionization mass spectrometry (ESI-MS) approaches were used to investigate the copper(II) coordination features of a new polyethylene glycol (PEG)-conjugated Abeta peptide fragment encompassing the 1-16 amino acid residues of the N-terminal region (Abeta(1-16)PEG). The high water solubility of the resulting metal complexes allowed us to obtain a complete complex speciation at different metal-to-ligand ratios ranging from 1:1 to 4:1. Potentiometric and ESI-MS data indicate that Abeta(1-16)PEG is able to bind up to four copper(II) ions. Furthermore, in order to establish the coordination environment at each metal binding site, a series of shorter peptide fragments of Abeta, namely, Abeta(1-4), Abeta(1-6), AcAbeta(1-6), and AcAbeta(8-16)Y10A, were synthesized, each encompassing a potential copper(II) binding site. The complexation properties of these shorter peptides were also comparatively investigated by using the same experimental approach.     

Synthesis of highly functionalised enantiopure bicyclo[3.2.1]- octane systems from carvone

The commercially available monoterpene carvone has been efficiently converted into the tricyclo[3.2.1.0(2.7)]octane and bicyclo[3.2.1]octane systems characteristic of some biologically active compounds. The sequence used for this transformation involves as key features an intramolecular Diels-Alder reaction of a 5-vinyl-1,3-cyclohexadiene and a cyclopropane ring opening.     

Synthetic Use of Dialkyl Phosphite/Carbon Tetrachloride Mixture in Inter-and Intramolecular Dehydrating Reactions

Abstract

Dialkyl phosphoryl chlorides generated “in situ” fiom dialkyl phosphites and CCL on the surface of solid KXO, in the presence of a PT catalyst can be used for activation of carboxylic acids via mixed anhydride formation and also for activation of ureas by the formation of 0-phosphoryl isourea derivatives. In M a reaction of the intermediates result in formation of amides and esters by the reaction of amine or alcohols, or in case of urea the derivative carbodide forming spontaneously by heat     

Synthesis of Sulfur-Containing Morphinane Dienes

6- and 7-thiocyanato derivatives of 6-demethoxythebaine were obtained by nucleophilic substitution and elimination reactions of 14-halogenated codeine tosylate.     

Reexamination of the power spectrum in de Sitter inflation

We find that the amplitude of quantum fluctuations of the invariant de Sitter vacuum coincides exactly with that of the vacuum of a comoving observer for a massless scalar (inflaton) field. We propose redefining the actual physical power spectrum as the difference between the amplitudes of the above vacua. An inertial particle detector continues to observe the Gibbons-Hawking temperature. However, although the resulting power spectrum is still scale-free, its amplitude can be drastically reduced since now, instead of the Hubble's scale at the inflationary period, it is determined by the square of the mass of the inflaton fluctuation field.     

Universal geometric entanglement close to quantum phase transitions

Under successive renormalization group transformations applied to a quantum state |Psi of finite correlation length xi, there is typically a loss of entanglement after each iteration. How good it is then to replace |Psi by a product state at every step of the process? In this Letter we give a quantitative answer to this question by providing first analytical and general proofs that, for translationally invariant quantum systems in one spatial dimension, the global geometric entanglement per region of size L>xi diverges with the correlation length as (c/12)log(xi/epsilon) close to a quantum critical point with central charge c, where is a cutoff at short distances. Moreover, the situation at criticality is also discussed and an upper bound on the critical global geometric entanglement is provided in terms of a logarithmic function of L.     

Efficient photovoltaic current generation at ferroelectric domain walls

We elucidate the mechanism of a newly observed photovoltaic effect which occurs in ferroelectrics with periodic domain structures. Under sufficiently strong illumination, domain walls function as nanoscale generators of the photovoltaic current. The steps in the electrostatic potential function to accumulate electrons and holes on opposite sides of the walls while locally reducing the concentration of the oppositely charged carriers. As a result, the recombination rate adjacent to the walls is reduced, leading to a net diffusion current. In open circuit, photovoltages for periodically ordered domain walls are additive and voltages much larger than the band gap can be generated. The internal quantum efficiency for individual domain walls can be surprisingly high, approaching 10% for above band-gap photons. Although we have found the effect in BiFeO(3) films, it should occur in any system with a similar periodic potential.     

Structural and optical properties of nanoparticulate Y2O3:Eu2O3 made by microwave plasma synthesis

Nanoparticulate Y₂O₃:Eu₂O₃ with a small, uniform particle size and a well-defined composition was synthesized using a low temperature microwave plasma process. The structural evolution and the luminescence properties were studied in different states of annealing and Eu₂O₃ addition using X-ray diffraction, transmission electron microscopy, and UV-photoluminescence spectroscopy. As synthesized, the samples were amorphous and showed only weak luminescence. Subsequent annealing steps from 500°C to 800°C lead to the formation and growth of cubic Y₂O₃:Eu₂O₃ nanocrystals (5–20 nm) and a concomitant strong increase of the luminescence yield already at small grain sizes in the range of 10 nm. No self-quenching effects were observed up to 11 mol% Eu₂O ₃.