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81.
Dr. Lisa Candish Lena Pitzer Dr. Adrián Gómez‐Suárez Prof. Dr. Frank Glorius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4753-4756
Described herein is a new and straightforward decarboxylative di‐ and trifluoromethylthiolation of alkyl carboxylic acids promoted by visible light. This approach enables the synthesis of biologically relevant alkyl SCF2H and SCF3 compounds from cheap and abundant carboxylic acids. The method is operationally simple, using irradiation from household light sources, and its mild reaction conditions make it tolerant of a range of functional groups. The strategy employs electrophilic phthalimide‐derived di‐ and trifluoromethylthiolation reagents and exploits the ability of the imidyl radical to carry a radical chain. 相似文献
82.
Dr. Małgorzata Walewska Dr. Judith Baumgartner Prof. Christoph Marschner Dr. Lena Albers Prof. Thomas Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(51):18512-18521
Silylated germylene–PMe3 adducts exchange their phosphane moiety smoothly for an N‐heterocyclic carbene or isocyanide species to form their respective base adducts. Reaction of the silylated germylene–PMe3 adducts with monosubstituted alkynes produce germylene adducts with the alkyne inserted into a Ge?Si bond. A computational study of this process provides evidence for the initial formation of a germirene, which rearranges to a vinylgermylene species. The thermodynamic driving force for this reaction is provided by subsequent adduct formation with PMe3. Reaction of the PMe3 adduct of bis[(trimethylsilyl)silyl]germylene with disubstituted alkynes leads to the formation of stable germirenes, which can be isomerized further to silagermetes. 相似文献
83.
The reactions of dipotassium germacyclopentadienediide with two Group 13 dichlorides, Cp*BCl2 and Cp*AlCl2, yield two structurally different products. In the case of boron a borole complex of germanium(ii) is obtained. The aluminium halide gives an unprecedented neutral germaaluminocene. Both compounds were fully characterised by multinuclear NMR spectroscopy supported by DFT computations. The molecular structure of the germaaluminocene was determined by XRD.Boron vs. aluminum: the synthesis of a borole complex of Ge(ii) is reported. Changing just the element from boron to aluminum unexpectedly yields an unprecedented neutral germaaluminocene. 相似文献
84.
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86.
A microwave-assisted, one-pot, iridium-catalyzed aromatic C-H borylation/rhodium-catalyzed 1,4-conjugate addition sequence provides a highly robust protocol suitable for high-throughput array synthesis. Selective formation of either β-aryl-substituted ketones or the corresponding alcohols can be achieved in good overall yields by simple variation of the reaction conditions. 相似文献
87.
Mohammad-Reza Zamani-Meymian Lena Jentjens Niels L. Raeth Konrad Peithmann Karl Maier 《Applied Physics A: Materials Science & Processing》2010,98(4):909-912
Irradiation of congruently melting, nominally undoped lithium niobate crystals (LiNbO3) with high-energy, low-mass 3He ions, which are transmitted through the crystal, causes large and stable changes of the refractive index. In the irradiated
regions, the extraordinary index is increased whereas the ordinary index is diminished. The decay of these changes upon annealing
treatments up to 400°C is investigated, exhibiting a strongly non-monoexponential decay behaviour. Long-term measurements
of the refractive index changes yield no pattern erasure on a timescale of four years. 相似文献
88.
Lena G Lallemand E Gruner AC Boeglin J Roussel S Schaffner AP Aubry A Franetich JF Mazier D Landau I Briand JP Didierjean C Rénia L Guichard G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(33):8498-8512
The development of the 1,3,5-triazepane-2,6-dione system as a novel, conformationally restricted, and readily accessible class of dipeptidomimetics is reported. The synthesis of the densely functionalized 1,3,5-triazepane-2,6-dione skeleton was achieved in only four steps from a variety of simple linear dipeptide precursors. To extend the practical value of 1,3,5-triazepane-2,6-diones, a general polymer-assisted solution-phase synthesis approach amenable to library production in a multiparallel format was developed. The conformational preferences of the 1,3,5-triazepane-2,6-dione skeleton were investigated in detail by NMR spectroscopy and X-ray diffraction. The ring exhibits a characteristic folded conformation which was compared to that of related dipeptide-derived scaffolds including the more planar 2,5-diketopiperazine (DKP). Molecular and structural diversity was increased further through post-cyclization appending operations at urea nitrogens. Preliminary biological screens of a small collection of 1,3,5-triazepane-2,6-diones revealed inhibitors of the underexplored malaria liver stage and suggest strong potential for this dipeptide-derived scaffold to interfere with and to modulate biological pathways. 相似文献
89.
Santos M de Matos AP Marçalo J Gibson JK Haire RG Tyagi R Pitzer RM 《The journal of physical chemistry. A》2006,110(17):5751-5759
Oxidation reactions of bare and ligated, monopositive, and dipositive Pa ions in the gas phase were studied by Fourier transform ion cyclotron resonance mass spectrometry. Seven oxidants were employed, ranging from the thermodynamically robust N(2)O to the relatively weak CH(2)O-all oxidized Pa(+) to PaO(+) and PaO(+) to PaO(2)(+). On the basis of experimental observations, it was established that D[Pa(+)-O] and D[OPa(+)-O] > or = 751 kJ mol(-1). Estimates for D[Pa(+)-O], D[OPa(+)-O], IE[PaO], and IE[PaO(2)] were also obtained. The seven oxidants reacted with Pa(2+) to produce PaO(2+), indicating that D[Pa(2+)-O] > or = 751 kJ mol(-1). A particularly notable finding was the oxidation of PaO(2+) by N(2)O to PaO(2)(2+), a species, which formally comprises Pa(VI). Collision-induced dissociation of PaO(2)(2+) suggested the protactinyl connectivity, {O-Pa-O}(2+). The experimentally determined IE[PaO(2)(+)] approximately 16.6 eV is in agreement with self-consistent-field and configuration interaction calculations for PaO(2)(+) and PaO(2)(2+). These calculations provide insights into the electronic structures of these ions and indicate the participation of 5f orbitals in bonding and a partial "6p hole" in the case of protactinyl. It was found that PaO(2)(2+) catalyzes the oxidation of CO by N(2)O-such O atom transport via a dipositive metal oxide ion is distinctive. It was also observed that PaO(2)(2+) is capable of activating H(2) to form the stable PaO(2)H(2+) ion. 相似文献
90.
Ding F Rosén A Campbell EE Falk LK Bolton K 《The journal of physical chemistry. B》2006,110(15):7666-7670
A new model is proposed for the encapsulation of catalyst metal particles by graphite layers that are obtained, for example, in low-temperature chemical vapor deposition production of carbon nanotubes (CNTs). In this model graphite layers are primarily formed from the dissolved carbon atoms in the metal-carbide particle when the particle cools. This mechanism is in good agreement with molecular dynamics simulations (which show that precipitated carbon atoms preferentially form graphite sheets instead of CNTs at low temperatures) and experimental results (e.g., encapsulated metal particles are found in low-temperature zones and CNTs in high-temperature regions of production apparatus, very small catalyst particles are generally not encapsulated, and the ratio of the number of graphitic layers to the diameter of the catalyst particle is typically 0.25 nm(-1)). 相似文献