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971.
Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction
Laurent Gavara Thomas Boisse Jean-Pierre Hénichart Adam Daïch Philippe Gautret 《Tetrahedron》2010,66(38):7544-5571
In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments. 相似文献
972.
Beata Kolesińska Katarzyna Kasperowicz Adam Mazur Zbigniew J. Kamiński 《Tetrahedron letters》2010,51(1):20-4513
The concept of a chiral coupling reagent for the enantioselective synthesis of peptides with a predictable configuration and enantiomeric purity from racemic substrates is presented. The reagent was prepared by treatment of strychninium tetrafluoroborate with 2-chloro-4,6-dimethoxy-1,3,5-triazine in the presence of sodium bicarbonate yielding N-(4,6-dimethoxy-1,3,5-triazin-2-yl)strychninium tetrafluoroborate in high yield, which is stable at room temperature, and in a broad range of solvents gave enriched Z-Ala-Phe-OMe (dr from 95/5 to 60/40) in high yield with d-configuration on the alanine residue starting from rac-Z-Ala-OH. 相似文献
973.
A simple, fast, reproducible (2.5% RSD at 3.0 μg/L), and sensitive method is described for quantifying As(III) (0.3 μg/L detection limit, 0.5–440 μg/L dynamic range). Anodic stripping voltammetry (ASV) is performed after accumulating arsenic at a mercury film electrode at ?0.350 V vs. Ag/AgCl (saturated KCl) for 20 s in 0.2 M HCl containing 8 μM ammonium 2‐amino‐1‐cyclopentene‐1‐dithiocarboxylate (AACD), without oxygen removal. This is the first report of using AACD in ASV and in electrochemical quantification of As(III). Total arsenic is determined after sodium‐sulfite‐reduction of As(V) to As(III). Interferences are minimal. Method validation involved water and metal alloy samples. 相似文献
974.
We introduce the intex density X(R,u), which combines both the intracular and extracular coordinates to yield a simultaneous probability density for the position of the center-of-mass radius (R) and relative separation (u) of electron pairs. One of the principle applications of the intex density is to investigate the origin of the recently observed secondary Coulomb hole. The Hartree-Fock (HF) intex densities for the helium atom and heliumlike ions are symmetric functions that may be used to prove the isomorphism 2I(2R)=E(R), where I(u) is the intracule density and E(R) is the extracule density. This is not true of the densities that we have constructed from explicitly correlated wave functions. The difference between these asymmetric functions and their symmetric HF counterparts produces a topologically rich intex correlation hole. From the intex hole distributions (X(exact)(R,u)-X(HF)(R,u)), we conclude that the probability of observing an electron pair with a very large interelectronic separation increases with the inclusion of correlation only when their center-of-mass radius is close to half of their separation. 相似文献
975.
McIntosh JA Robertson CR Agarwal V Nair SK Bulaj GW Schmidt EW 《Journal of the American Chemical Society》2010,132(44):15499-15501
A protease from ribosomal peptide biosynthesis macrocyclizes diverse substrates, including those resembling nonribosomal peptide and hybrid polyketide-peptide products. The proposed mechanism is analogous to thioesterase-catalyzed chemistry, but the substrates are amide bonds rather than thioesters. 相似文献
976.
Adam Neuba Dr. Sonja Herres‐Pawlis Oliver Seewald Janna Börner Andreas J. Heuwing Ulrich Flörke Prof. Dr. Gerald Henkel 《无机化学与普通化学杂志》2010,636(15):2641-2649
The transition metal complexes with the ligand 1,3‐bis(N,N,N′,N′‐tetramethylguanidino)propane (btmgp), [Mn(btmgp)Br2] ( 1 ), [Co(btmgp)Cl2] ( 2 ), [Ni(btmgp)I2] ( 3 ), [Zn(btmgp)Cl2] ( 4 ), [Zn(btmgp)(O2CCH3)2] ( 5 ), [Cd(btmgp)Cl2] ( 6 ), [Hg(btmgp)Cl2] ( 7 ) and [Ag2(btmgp)2][ClO4]2·2MeCN ( 8 ), were prepared and characterised for the first time. The stoichiometric reaction of the corresponding water‐free metal salts with the ligand btmgp in dry MeCN or THF resulted in the straightforward formation of the mononuclear complexes 1 – 7 and the binuclear complex 8 . In complexes with MII the metal ion shows a distorted tetrahedral coordination whereas in 8 , the coordination of the MI ion is almost linear. The coordination behavior of btmgp and resulting structural parameters of the corresponding complexes were discussed in an comparative approach together with already described complexes of btmgp and the bisguanidine ligand N1,N2‐bis(1,3‐dimethylimidazolidin‐2‐ylidene)‐ethane‐1,2‐diamine (DMEG2e), respectively. 相似文献
977.
L. B. Belykh N. I. Skripov L. N. Belonogova V. A. Umanets F. K. Schmidt 《Kinetics and Catalysis》2010,51(1):42-49
The applicability of elemental phosphorus as a modifier of palladium catalysts for hydrogenation was demonstrated, and the
conditions for the synthesis of nanoparticles that are highly efficient in hydrogenation catalysis were optimized. The modifying
effect of elemental phosphorus depends on the P/Pd ratio; it is associated with changes in the catalyst dispersity and the
nature of the formed nanoparticles containing various palladium phosphides (PdP2, Pd5P2, and Pd6P) and Pd(0) clusters. The main stages of the formation of palladium catalysts for hydrogenation were determined, and a model
of an active catalyst, in which the Pd6P phosphide is the core of a nanoparticle and Pd(0) clusters form a shell, was proposed. 相似文献
978.
A. F. Schmidt A. A. Kurokhtina A. N. Svechkarev V. V. Smirnov A. Al-Halaiqa 《Kinetics and Catalysis》2010,51(1):113-118
The results of comparative kinetic experiments, homogeneity/heterogeneity testing data, and the relative substrate reactivity
data for the Suzuki and Heck reactions are consistent with the participation of heterogeneous forms of the catalyst (colloidal
palladium and larger palladium aggregates) in the Suzuki reaction. This is the reason why the Suzuki reaction occurs more
readily than the Heck reaction. The data obtained in this study indicate that these reactions differ in the nature of catalyst
deactivation processes. 相似文献
979.
Adam A. Stokes David J. Clarke Stefan Weidt Pat Langridge-Smith C. Logan Mackay 《International journal of mass spectrometry》2010,289(1):54-57
We report high resolution spectra for the medium molecular weight proteins myoglobin and cytochrome-c obtained using a custom desorption electrospray ionisation (DESI) source coupled to a Bruker Daltonics 12 T Apex Qe Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS). The DESI source was designed for accurate alignment and reproduction of critical geometric variables. A two axis motorised stage was included to enable automated rastering of the sample under the DESI plume. Spectra for the intact proteins have been obtained under single-acquisition conditions and a top-down analysis of cytochrome-c was performed using both collision induced dissociation (CID) and electron capture dissociation (ECD) of the isolated [M+15H]15+ charge state. The sequence coverage is comparable to that obtained using electrospray ionisation, demonstrating the utility of top-down protein analysis by DESI FTICR-MS. 相似文献
980.
Chao Jin Chenghao Yang Fei Zhao Adam Coffin Fanglin Chen 《Electrochemistry communications》2010,12(10):1450-1452
Cu1.3Mn1.7O4 spinel oxide has been synthesized and characterized as anode internal reforming layer for Ni–SDC anode-supported solid oxide fuel cells (SOFCs) directly operating on methane fuel. XRD and Cu mapping image results of Cu1.3Mn1.7O4 oxide after in-situ reduction by methane show that a highly dispersed nano-Cu metal network has been obtained. By adopting Cu1.3Mn1.7O4 as an internal reforming layer, the cell demonstrated maximum power densities of 242 and 311 mW cm?2 at 650 and 700 °C, respectively using methane as fuel and ambient air as oxidant. More importantly, Cu1.3Mn1.7O4 internal reforming layer has significantly improved the cell performance stability. The cell with the Cu1.3Mn1.7O4 internal reforming layer has demonstrated reasonably stable performance while the cell without it degraded very rapidly. 相似文献