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The development of catalysts capable of catalyzing amidation of esters with amines to construct amides under mild conditions is of great importance. Compared to aliphatic amines, the direct catalytic amidation of esters with less nucleophilic aromatic amines is rather difficult. Employing simple lanthanide tris (amide) complexes Ln[N (SiMe3)2]3(μ-Cl)Li (THF)3 as the catalysts, it was found a broad range of aromatic amines and esters were efficiently converted into various amides in good yields under mild conditions. A plausible mechanism for this transformation was experimentally supported as starting from an amide exchange reaction between the lanthanide tris (amide) complex and the substrate amine. 相似文献
34.
Naghmeh Esfandiary Farzane Pazoki Athar Nakisa Kobra Azizi Iman Radfar Akbar Heydari 《应用有机金属化学》2020,34(8):e5725
A highly efficient Fe3O4@VitB1–Ag(I) magnetic catalyst has been obtained using surface modification of Fe3O4. To this end, silver chloride was immobilized on Fe3O4 nanoparticles via vitamin B1 biomolecules. The synthesized biocompatible magnetic catalyst was applied in an A3-coupling reaction in the presence of aldehyde, amine and phenyl acetylene under solvent-free conditions and afforded the desired products in excellent yields. Also, interactions between metal and ligand in the Fe3O4@VitB1–Ag(I) were studied using theoretical calculations. 相似文献
35.
In the present work we characterize the existence of quasistationary distributions for diffusions on allowing singular behavior at 0 and . If absorption at 0 is certain, we show that there exists a quasistationary distribution as soon as the spectrum of the generator is strictly positive. This complements results of Cattiaux et al. (2009) and Kolb and Steinsaltz (2012) for 0 being a regular boundary point and extends results by Cattiaux et al. (2009) on singular diffusions. 相似文献
36.
Taichi Koike Dr. Tomoyuki Kosai Prof. Dr. Takeaki Iwamoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(39):9295-9302
Cyclic (alkyl)(amino)silylene (CAASi) 1 has been found to successfully dehydrogenate 1,4-dihydroaromatic compounds containing various substituents to afford the corresponding aromatic compounds. The observed high substrate generality proves 1 to be a potential 1,4-dehydrogenation reagent for organic compounds. For the reaction with 9,10-dimethyl-9,10-dihydroanthracene, silylene 1 activated not only benzylic C−H bonds but also aromatic C−H bonds to yield a silaacenaphthene derivative, which is an unprecedented reaction of silylenes. The results of the experimental and computational study of the reaction of CAASi 1 with 9,10-dihydroanthracene and 1,4-cyclohexadiene are consistent with the notion that 1,4-dehydrogenation with CAASi 1 proceeds mainly through a stepwise hydrogen-abstraction mechanism. 相似文献
37.
Dr. Yago García-Rodeja Prof. Dr. Israel Fernández 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(41):9771-9779
The influence of the replacement of C=C bonds by isoelectronic B−N moieties on the reactivity of π-curved polycyclic aromatic hydrocarbons has been computationally explored by means of density functional theory calculations. To this end, we selected the Diels–Alder cycloaddition reactions of the parent corannulene and its BN-doped counterparts with either cyclopentadiene or maleic anhydride. In addition, the analogous reactions involving larger buckybowls, such as BN-hemifullerene, BN-circumtrindene, and BN-fullerene, have been also considered. It has been found that whereas corannulene behaves as a dienophile, its BN counterpart better acts as a diene. In contrast, the larger BN-curved systems cannot be used as dienes in Diels–Alder reactions, but undergo facile (i.e., low barrier) cycloaddition reactions with cyclopentadiene. The observed trends in reactivity, which cannot be directly explained by using typical frontier molecular orbital arguments, are quantitatively described in detail by means of state-of-the-art computational methods, namely the activation strain model of reactivity combined with the energy decomposition analysis method. The results of our calculations highlight the crucial role of the curvature of the system on the reactivity and its influence on the strength of the orbital interactions between the deformed reactants during their transformations. 相似文献
38.
Ion Grama Ronan Lauvergnat Émile Le Page 《Stochastic Processes and their Applications》2019,129(7):2485-2527
Let be a branching process in a random environment defined by a Markov chain with values in a finite state space . Let be the probability law generated by the trajectories of starting at We study the asymptotic behaviour of the joint survival probability , as in the critical and strongly, intermediate and weakly subcritical cases. 相似文献
39.
Thomas Mikosch Mohsen Rezapour Olivier Wintenberger 《Stochastic Processes and their Applications》2019,129(11):4638-4662
In this paper we consider a stochastic model of perpetuity-type. In contrast to the classical affine perpetuity model of Kesten (1973) and Goldie (1991) all discount factors in the model are mutually independent. We prove that the tails of the distribution of this model are regularly varying both in the univariate and multivariate cases. Due to the additional randomness in the model the tails are not pure power laws as in the Kesten–Goldie setting but involve a logarithmic term. 相似文献
40.
Poly (ether ether ketone) was irradiated with gamma rays or electron beam to investigate the radical process. The generated paramagnetic species were observed by electron spin resonance spectroscopy at ambient temperature and in liquid nitrogen. The effect of microwave power on saturation of the particular spectra and thermal annealing effects were determined. The following radicals were identified: radical anion, phenoxyl radical, and phenylperoxy radical. Despite the fact that the intermediates were formed as a result of backbone cleavage causing degradation, the macroscopic features were almost unaffected by irradiation up to dose of 1500 kGy. 相似文献