Basic CuCO3/ligand as a new catalyst for 'on water' borylation of Michael acceptors,alkenes and alkynes: application to the efficient asymmetric synthesis of β‐alcohol type sitagliptin side chain

The efficient 'on water' β‐borylation using bis(pinacolato)diboron agent was achieved with a newly developed catalytic system based on basic copper carbonate and various ligands. The catalytic system was used for β‐borylation of various Michael acceptors, alkenes and alkynes. The presented methodology was successfully applied to the novel synthesis of β‐alcohol type sitagliptin side chain precursor via water‐based highly enantioselective β‐borylation followed by an oxidation process. Copyright © 2013 John Wiley & Sons, Ltd.     

CYANOS: a data management system for natural product drug discovery efforts using cultured microorganisms

A software package, termed "CYANOS", has been developed to facilitate the data management and mining for natural product drug discovery efforts. This system allows for the management of data associated with field collections, culture conditions, harvests, extractions, chemical separations, and biological evaluation. This software utilizes a MySQL database for data storage, which allows for reporting and data mining via third party tools. In addition, a Web-based interface was constructed to allow for multiuser access from a variety of desktop platforms. The code for this system is freely available and has been released under the Illinois Open Source license.     

5,10:13,14-Disecosteroids: novel modified steroids containing 10- and 9-membered rings

In this paper a synthetic pathway to the modified 5,10:13,14-bisfragmentation cholestane derivatives 8-14 is described. The synthesis involves introduction of the 5α- and 14α-hydroxyl groups in the cholestane molecule and subsequent cleavage of the C(5)-C(10) bond in 5α,14α-dihydroxycholestan-3β-yl acetate (4) with the HgO/I₂ reagent and the C(13)-C(14) bond in the stereoisomeric 14α-hydroxy-5,10-secosteroids 5 and 6 with the Pb(OAc)₄/I₂ reagent. Complete and unambiguous ¹H and ¹³C NMR resonance assignments of the obtained secosteroids, as well as the solution conformations of their 10- and 9-membered rings were determined by extensive analysis of 1D and 2D NMR spectral data. The structures and the solid-state conformations of 5,10-secosteroids 5-7 were confirmed by X-ray analysis. All diseco-compounds have a novel 5,10:13,14-disecocholestane skeleton.     

Nitrile-Containing Fischerindoles from the Cultured Cyanobacterium Fischerella sp

Chemical investigation of the cultured cyanobacterium Fischerella sp. (SAG strain number 46.79) led to the isolation of four nitrile-containing indole alkaloids, namely 12-epi-fischerindole I nitrile (1), deschloro 12-epi-fischerindole I nitrile (2), 12-epi-fischerindole W nitrile (3), and deschloro 12-epi-fischerindole W nitrile (4) along with a known metabolite hapalosin. The structures were determined by detailed spectroscopic analyses on the basis of 1D and 2D NMR and HRESIMS data. All isolates were evaluated for cytotoxicity against human cancer cells and for 20S proteasome inhibition. Deschloro 12-epi-fischerindole I nitrile (2) was found to be weakly cytotoxic against HT-29 cells with an ED(50) value of 23 μM. Hapalosin showed weak cytotoxicity against HT-29 and MCF-7 cells with ED(50) values of 22 and 27 μM, respectively, as well as moderate 20S proteasome inhibition with an IC(50) value of 12 μM. Compounds 1-4 all contain a nitrile moiety instead of the isonitrile found in all fischerindoles reported to date. Compounds 3 and 4 also display a new carbon skeleton, in which a six-membered ring replaces the five-membered ring normally found in fischerindole-type alkaloids.     

Probabilities of high excursions of Gaussian fields

Let {ξ(t), t ∈ T} be a differentiable (in the mean-square sense) Gaussian random field with E ξ(t) ≡ 0, D ξ(t) ≡ 1, and continuous trajectories defined on the m-dimensional interval T ì \mathbbR^m T \subset {\mathbb{R}^m} . The paper is devoted to the problem of large excursions of the random field ξ. In particular, the asymptotic properties of the probability P = P{−v(t) < ξ(t) < u(t), t ∈ T}, when, for all t ∈ T, u(t), v(t) ⩾ χ, χ → ∞, are investigated. The work is a continuation of Rudzkis research started in [R. Rudzkis, Probabilities of large excursions of empirical processes and fields, Sov. Math., Dokl., 45(1):226–228, 1992]. It is shown that if the random field ξ satisfies certain smoothness and regularity conditions, then P = e^−Q  + Qo(1), where Q is a certain constructive functional depending on u, v, T, and the matrix function R(t) = cov(ξ′(t), ξ′(t)).     

Investigation of Structural and Luminescent Properties of Sol-Gel-Derived Cr‑Substituted Mg3Al1−xCrx Layered Double Hydroxides

In the present work, Cr-substituted Mg₃Al_1−xCr_x layered double hydroxides (LDHs) were synthesised through the phase conversion of sol-gel-derived mixed-metal oxides in an aqueous medium. The chromium substitution level in the range of 1 to 25 mol% was investigated. It was demonstrated that all synthesised specimens were single-phase LDHs. The results of elemental analysis confirmed that the suggested synthetic sol-gel chemistry approach is suitable for the preparation of LDHs with a highly controllable chemical composition. The surface microstructure of sol-gel-derived Mg₃Al_1−xCr_x LDHs does not depend on the chromium substitution level. The formation of plate-like agglomerated particles, which consist of hexagonally shaped nanocrystallites varying in size from approximately 200 to 300 nm, was observed. Optical properties of the synthesised Mg₃Al_1−xCr_x LDHs were investigated by means of photoluminescence. All Cr-containing powders exhibited characteristic emission in the red region of the visible spectrum. The strongest emission was observed for the sample doped with 5 mol% Cr³⁺ ions. However, the emission intensity of samples doped with 1–10 mol% Cr³⁺ ions was relatively similar. A further increase in the Cr³⁺ ion concentration to 25 mol% resulted in severe concentration quenching.     

Spin dynamics in Cd1−xMnx Te studied by muon spin rotation

Spin fluctuations in Cd_1−xMn_xTe (x=0.05, 0.10, 0.20, 0.30, 0.40, 0.54, 0.60, 0.68) were studied by the muon spin rotation (μSR) technique. Correlation times of the Mn-spins are deduced from the muon depolarization rates. A strong increase of the depolarization rate near the Mn-spin freezing temperature is observed. At 88 K, larger depolization rates are found forx=0.10 andx=0.20 than for higher Mn-concentrations, indicating that the exchange narrowing is considerably reduced (spin fluctuations slow down) for lower Mn-concentrations.