The catalytic enantioselective hydroamination–hydroarylation of alkynes under the catalysis of (R3P)AuMe/(S)‐3,3′‐bis(2,4,6‐triisopropylphenyl)‐1,1′‐binaphthyl‐2,2′‐diyl hydrogenphosphate ((S)‐TRIP) is reported. The alkyne was reacted with a range of pyrrole‐based aromatic amines to give pyrrole‐embedded aza‐heterocyclic scaffolds bearing a quaternary carbon center. The presence of a hydroxyl group in the alkyne tether turned out to be very crucial for obtaining products in high yields and enantioselectivities. The mechanism of enantioinduction was established by carefully performing experimental and computational studies. 相似文献
The use of ynamides in organic synthesis has gained significant attention due to their ability to provide access to complex molecular structures through transformations such as 1,2-difunctionalization and annulation reactions. These reactions enable the formation of highly functionalized N-bearing olefins and unusual N-bearing heterocycles. In this minireview, we present a systematic overview of the regioselective difunctionalization and annulation reactions of ynamides. We discuss the multi-component reactions, and radical-triggered functionalizations across the ynamides carbon–carbon multiple bonds and the use of bifunctional reagents in annulation of ynamides, highlighting their potential in expanding the substrate scope. Furthermore, we provide insights into the mechanistic breakthroughs that have been achieved in recent years in the development of these reactions. Finally, we emphasize the promising future prospects of ynamides as versatile building blocks for the synthesis of complex molecular architectures. 相似文献
Herein, we report the first synthesis of an unorthodox tripyrrane moiety from the regioselective β‐benzoylation of pyrrole and the acid‐catalyzed condensation of the desired precursors. A [3+1] Mac Donald type condensation strategy for this tripyrrane has led to the exclusive isolation of two hitherto‐unknown aromatic [20] heterocyclic macrocycles (4.1.1). 相似文献
The layered compound LiCoO2 belonging to the ABO2 class exhibits a variety of interesting behaviors, and substitution adds a twist to the properties. Hence, the effect of partial substitution of Co+3 with Fe+3 on the high-temperature thermoelectric properties has been studied in detail. The X-ray diffraction patterns together with Rietveld refinement indicate formation of a single phase conforming to R\( \overset{-}{3} \)m space group in all the three cases, LiCo1?xFexO2 with x = 0.01, 0.02, and 0.08. The electrical resistivity in all the compounds decreases by four orders of magnitude with increasing temperature from 300 to 1000 K, a semiconducting behavior. The Seebeck coefficient is found to be very high, >700 μV K?1 in all the cases, and increases with increasing temperature and Fe+3 substitution. The thermal conductivity, on the other hand, has been found to decrease with temperature in all the compounds from 3.5 W m?1 K?1 at room temperature to 1 W m?1 K?1 at 973 K, a consequence of phonon-phonon scattering. High resistivity of the compounds limits power factor indicating that carrier concentration and mobility need to be increased to realize a high figure-of-merit. 相似文献
In this work we construct the stationary measure of the N species totally asymmetric simple exclusion process in a matrix product formulation. We make the connection between the matrix
product formulation and the queueing theory picture of Ferrari and Martin. In particular, in the standard representation,
the matrices act on the space of queue lengths. For N>2 the matrices in fact become tensor products of elements of quadratic algebras. This enables us to give a purely algebraic
proof of the stationary measure which we present for N=3. 相似文献
NiO thin films grown on Si (100) substrate by electron beam evaporation method and sintered at 700 °C were irradiated with 200 MeV Au15+ ions. The fcc structure of the sintered films was retained up to the highest fluence (1×1013 ions cm?2) of irradiation. However the microstructure of the pristine film underwent a considerable modification with increasing ion fluence. 200 MeV Au ion irradiation led to compressive stress generation in NiO medium. The diameter of the stressed region created by 200 MeV Au ions along the ion path was estimated from the variation of stress with ion fluence and found to be ~11.6 nm. The film surface started cracking when irradiated at and above the fluence of 3×1012 ions cm?2. Ratio of the fractal dimension of the cracked surface obtained at 200 MeV and 120 MeV (Mallick et al., 2010a) Au ions was compared with the ratio of the radii of ion tracks calculated based on Coulomb explosion and thermal spike models. This comparison indicated applicability of thermal spike model for crack formation. 相似文献
The structure of polymeric carbon dioxide (CO2-V) has been solved using synchrotron x-ray powder diffraction, and its evolution followed from 8 to 65 GPa. We compare the experimental results obtained for a 100% CO2 sample and a 1 mol?% CO2/He sample. The latter allows us to produce the polymer in a pure form and study its compressibility under hydrostatic conditions. The high quality of the x-ray data enables us to solve the structure directly from experiments. The latter is isomorphic to the β-cristobalite phase of SiO2 with the space group I42d. Carbon and oxygen atoms are arranged in CO4 tetrahedral units linked by oxygen atoms at the corners. The bulk modulus determined under hydrostatic conditions, B0=136(10) GPa, is much smaller than previously reported. The comparison of our experimental findings with theoretical calculations performed in the present and previous studies shows that density functional theory very well describes polymeric CO2. 相似文献
We investigate the growth of a crystal that is built by depositing cubes inside a corner. The interface of this crystal approaches a deterministic growing limiting shape in the long-time limit. Building on known results for the corresponding two-dimensional system and accounting for basic three-dimensional symmetries, we conjecture a governing equation for the evolution of the interface profile. We solve this equation analytically and find excellent agreement with simulations of the growth process. We also present a generalization to arbitrary spatial dimension. 相似文献
Photophysical properties of two widely used antibiotic fluoroquinolone drugs, namely Norfloxacin (NOR) and Ofloxacin (OFL) have been investigated in biomimicking environments formed by bile salts. Experimental results demonstrate that photophysical enhancement and fall of a particular prototropic species are sensitive to the excitation wavelength in bile salt aggregates. Excitation at shorter wavelengths reveals quenching of fluorescence of these fluoroquinolone with addition of sodium deoxycholate (NaDC), sodium taurocholate (NaTC) and sodium glycodeoxycholate (NaGDC). On the contrary, we observe a steady increase in the fluorescence intensity with a continuous redshift upon excitation at longer wavelength. The experimental results were rationalized in terms of the fact that, neutral and zwitterionic species of fluoroquinolone molecules in bile salt aggregates are selectively excited at shorter wavelength while the cationic form of fluoroquinolone molecules are excited at longer wavelength. The excess hydronium ions in the hydrophilic surface of bile salt aggregates convert the neutral species of NOR and OFL into cationic species causing an enhancement in the emission intensity. We found that NaGDC and NaTC because of the conjugate head group are more effective in converting the neutral species of fluoroquinolones into a cationic species than NaDC. The quenching order is in accordance with hydrophobicity indices of bile salt. 相似文献
Summary: We report a new method for the preparation of polyaniline nanoballs by using HAuCl4 as an oxidizing agent. During the reaction, aniline is oxidized and forms polyaniline whilst the hydrogen tetrachloroaurate is reduced and forms gold nanoparticles. These gold nanoparticles are found to decorate the nanoballs.
The resultant precipitate and corresponding TEM image of the gold‐nanoparticle covered polyaniline nanoball. 相似文献