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Total synthesis of (+/-)fasicularin via a 2-amidoacrolein cycloaddition

The total synthesis of the cytotoxin fasicularin is described. The key steps include the following: (1) an intermolecular Diels-Alder cycloaddition of a 2-(triflamido)acrolein with the dioxolane ketal of trideca-1,3-dien-7-one to establish the trans-perhydroisoquinoline stereochemistry, (2) a stereoelectronically controlled hydride addition to a N(1)-C(2) iminium ion to introduce the equatorial hexyl substituent, and (3) elaboration of the pyrido ring by an internal aldol reaction.     

m-Iodosylbenzoic Acid: Recyclable Hypervalent Iodine Reagent for α-Tosyloxylation and α-Mesyloxylation of Ketones

m-Iodosylbenzoic acid–mediated reactions of various carbonyl compounds provided α-organosulfonyloxy carbonyl compounds in good yields. The final products could be easily isolated without any chromatographic purification by simple treatment of the crude mixture with an anionic exchange resin.     

Constraining dark matter models from a combined analysis of Milky Way satellites with the Fermi Large Area Telescope

Satellite galaxies of the Milky Way are among the most promising targets for dark matter searches in gamma rays. We present a search for dark matter consisting of weakly interacting massive particles, applying a joint likelihood analysis to 10 satellite galaxies with 24 months of data of the Fermi Large Area Telescope. No dark matter signal is detected. Including the uncertainty in the dark matter distribution, robust upper limits are placed on dark matter annihilation cross sections. The 95% confidence level upper limits range from about 10(-26) cm3 s(-1) at 5 GeV to about 5×10(-23) cm3 s(-1) at 1 TeV, depending on the dark matter annihilation final state. For the first time, using gamma rays, we are able to rule out models with the most generic cross section (～3×10(-26) cm3 s(-1) for a purely s-wave cross section), without assuming additional boost factors.     

Total synthesis of (±)-cortistatin J from furan

A concise, diastereoselective total synthesis of (±)-cortistatin J has been completed in 20 steps from furan. Key steps include an intramolecular [4 + 3] cyclization of a disubstituted furan with a (Z)-2-(trialkylsilyloxy)-2-enal to construct the tetracyclic core and a (Z)-vinylsilane/iminium ion cyclization to form the A ring.     

Asymmetric first‐order transition and interlocked particle state in magnetocaloric La(Fe,Si)13

In‐situ synchrotron XRD measurements of the magnetocaloric material LaFe_11.8Si_1.2 are used to understand virgin effects and asymmetry of the underlying first order magnetovolume transition. A remarkable change of the transition kinetics occurs after the first cycle, which we attribute to the formation of cracks originating from the volume change. Tomographic imaging revealed that the bulk material disintegrates via an interlocked state where fragments are loosely connected. Though cracks have opened between the fragments, the transition is sharp, which we attribute to magnetostatic interactions. In the cycled sample we find a strong asymmetry between the transition interval upon heating and cooling, which we explain by isostatic pressure acting on parts of the sample during the cooling transition. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Adsorption dynamics of CO2 on Cu(1 1 0): A molecular beam study

Molecular beam scattering measurements have been conducted to examine the adsorption dynamics of CO₂ on Cu(1 1 0). The initial adsorption probability, S₀, decreases exponentially from 0.43 ± 0.03 to a value close to the detection limit (∼0.03) within the impact energy range of E_i = (0.12-1.30) eV. S₀ is independent of the adsorption temperature, T_s, and the impact angle, α_i, i.e., the adsorption is non-activated and total energy scaling is obeyed. The coverage, Θ, dependent adsorption probability, S(Θ), agrees with precursor-assisted adsorption dynamics (Kisliuk type) above T_s ∼ 91 K. However, below that temperature adsorbate-assisted adsorption (S increases with Θ) has been observed. That effect is most distinct at large E_i and low T_s. The S(Θ) data have been modeled by Monte Carlo simulations. No indications of CO₂ dissociation were obtained from Auger Electron Spectroscopy or the molecular beam scattering data.