The palladium‐catalyzed reaction of 2‐alkynylanilines with 2‐(2‐bromobenzylidene)cyclobutanone as an efficient route to 7,8‐dihydrobenzo[b]naphtho[2,3‐d]azocin‐6(5 H)‐ones was developed. The fused eight‐membered ring was constructed conveniently. During the reaction process, double carbometalation was involved, which resulted in excellent selectivity with the formation of three new bonds. This transformation is highly efficient and leads to fused polycycles in good to excellent yields with good functional group tolerance. 相似文献
Phosphine‐catalyzed enantioselective annulation reactions involving ketimines are a daunting synthetic challenge owing to the intrinsic low reactivity of ketimine substrates. A highly enantioselective [3+2] cycloaddition reaction that makes use of isatin‐derived ketimines as reaction partners was developed. Notably, both simple and γ‐substituted allenoates could be utilized, and various 3,2′‐pyrrolidinyl spirooxindoles with a tetrasubstituted stereocenter were obtained in excellent yields and with nearly perfect enantioselectivity (>98 % ee in all cases). 相似文献
The title complex [(C12H8N2)2Bi(O2NO)3] was synthesized by reaction of 1,10-phenanthroline (phen) and Bi(NO3)3·5H2O. The structure of the complex was characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. An advanced solution-reaction isoperibol microcalorimeter was applied to determine the standard molar enthalpies of formation at 298.15 K of the complex and Bi(NO3)3·5H2O, giving –(798.92 ± 5.99) and –(1986.87 ± 0.20) kJ mol−1, respectively. The biological effect of the complex was evaluated by microcalorimetry on the growth of Schizosaccharomyces pombe (S. pombe). According to thermogenic curves, the corresponding thermokinetics and thermodynamic parameters were derived. The complex had good bioactivity on the growth metabolism of S. pombe, with the value of IC50 being 2.8 × 10−5 mol L−1.
The resonance Rayleigh light-scattering (RRLS) signal of a new triazene reagent; 1-(o-nitrophenyl)-3-(2-thiazolyl)triazene (o-NPTT), was firstly synthesized and characterized in this paper at 500-600 nm wavelength range and can be enhanced remarkably by Pd2+. According to this phenomenon, a new method was developed for the determination of Pd2+ by the RRLS technique in the presence of Tween-80. The calibration graph showed good linearity over a concentration range of 5.0-700 microg l(-1) with a detection limit of 1.0 microg l(-1). There are almost no foreign ions interfered in the determination at a more than fivefold concentration of Pd2+. The method is relatively sensitive, of good selectivity and has been successfully used for the determination of trace palladium in the slag of fertilizer factories and catalyst samples. 相似文献
The title complex, C14H20O4S8+.BF4?, is a charge‐transfer complex with typical charges for the donor and anion of +1 and ?1, respectively. Two centrosymmetrically related donors form a face‐to‐face π‐dimer with a strong intermolecular S?S interaction. These π‐dimers stack along the a axis to form a donor column. The structure is extensively hydrogen bonded. 相似文献
A matrix-assisted laser desorption/ionization Fourier transform mass spectrometry (MALDI-FTMS)-based assay was developed for
kinetic measurements and inhibitor screening of acetylcholinesterase. Here, FTMS coupled to MALDI was applied to quantitative
analysis of choline using the ratio of choline/acetylcholine without the use of additional internal standard, which simplified
the experiment. The Michaelis constant (Km) of acetylcholinesterase (AChE) was determined to be 73.9 μmol L−1 by this approach. For Huperzine A, the linear mixed inhibition of AChE reflected the presence of competitive and noncompetitive
components. The half maximal inhibitory concentration (IC50) value of galantamine obtained for AChE was 2.39 μmol L−1. Inhibitory potentials of Rhizoma Coptidis extracts were identified with the present method. In light of the results the
referred extracts as a whole showed inhibitory action against AChE. The use of high-resolution FTMS largely eliminated the
interference with the determination of ACh and Ch, produced by the low-mass compounds of chemical libraries for inhibitor
screening. The excellent correlation with the reported kinetic parameters confirms that the MS-based assay is both accurate
and precise for determining kinetic constants and for identifying enzyme inhibitors. The obvious advantages were demonstrated
for quantitative analysis and also high-throughput characterization. This study offers a perspective into the utility of MALDI-FTMS
as an alternate quantitative tool for inhibitor screening of AChE. 相似文献
A de novo preparation of alpha-keto-imides via ynamide oxidation is described. With a number of alkyne oxidation conditions screened, a highly efficient RuO2-NaIO4 mediated oxidation and a DMDO oxidation have been identified to tolerate a wide range of ynamide types. In addition to accessing a wide variety of alpha-keto-imides, the RuO2-NaIO4 protocol provides a novel entry to the vicinal tricarbonyl motif via oxidation of push-pull ynamides, and imido acylsilanes from silyl-substituted ynamides. Chemoselective oxidation of ynamides containing olefins can be achieved by using DMDO, while the RuO2-NaIO4 protocol is not effective. These studies provide further support for the synthetic utility of ynamides. 相似文献
This report describes routes to iron dithiolato carbonyls that do not require preformed iron carbonyls. The reaction of FeCl 2, Zn, and Q 2S 2C n H 2 n (Q (+) = Na (+), Et 3NH (+)) under an atmosphere of CO affords Fe 2(S 2C n H 2 n )(CO) 6 ( n = 2, 3) in yields >70%. The method was employed to prepare Fe 2(S 2C 2H 4)( (13)CO) 6. Treatment of these carbonylated mixtures with tertiary phosphines, instead of Zn, gave the ferrous species Fe 3(S 2C 3H 6) 3(CO) 4(PR 3) 2, for R = Et, Bu, and Ph. Like the related complex Fe 3(SPh) 6(CO) 6, these compounds consist of a linear arrangement of three conjoined face-shared octahedral centers. Omitting the phosphine but with an excess of dithiolate, we obtained the related mixed-valence triiron species [Fe 3(S 2C n H 2 n ) 4(CO) 4] (-). The highly reducing all-ferrous species [Fe 3(S 2C n H 2 n ) 4(CO) 4] (2-) is implicated as an intermediate in this transformation. Reactive forms of iron, prepared by the method of Rieke, also combined with dithiols under a CO atmosphere to give Fe 2(S 2C n H 2 n )(CO) 6 in modest yields under mild conditions. Studies on the order of addition indicate that ferrous thiolates are formed prior to the onset of carbonylation. Crystallographic characterization demonstrated that the complexes Fe 3(S 2C 3H 6) 3(CO) 4(PEt 3) 2 and PBnPh 3[Fe 3(S 2C 3H 6) 4(CO) 4] feature high-spin ferrous and low-spin ferric as the central metal, respectively. 相似文献