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111.
Christopher Lombardi Dr. Richard P. Rucker Dr. Robert D. J. Froese Dr. Sepideh Sharif Prof. Pier Alexandre Champagne Prof. Michael G. Organ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(62):14223-14229
The relative rates of arylation of primary alkylamines with different Pd-NHC catalysts have been measured, as have the relative rates of arylation of the secondary aniline product in an attempt to understand the key ligand design features necessary to have high selectivity for the monoarylated amine product. As the substituents on the N-aryl ring of the NHC increase in size, selectivity for monoarylation increases and this is further enhanced by chlorinating the back of the NHC ring. Computations have been performed on the catalytic cycle of this transformation in order to understand the selectivity obtained with the different catalysts. 相似文献
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Xu‐Wen Li Alexandre Ear Lukas Roger Dr. Nassima Riache Alexandre Deville Dr. Bastien Nay 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16389-16393
A bio‐inspired strategy was used to complete the formal synthesis of the antitubercular hirsutellone B and congeners A and C, through construction of its decahydrofluorene core from a linear polyene strand activated at both ends by a silyl enol ether and an allyl acetate. Our synthesis features a key electrophilic cyclization, starting with the remote activation (by [Yb(OTf)3] or BF3 ? OEt2) of the allyl acetate and stereoselectively affording the C ring. This was followed by an intramolecular Diels–Alder reaction to get the tricyclic core of the natural product. The stereoselective reduction of the resulting ketone towards the formal intermediate was critical to the success of this strategy. 相似文献
114.
We have studied the effect of interface heterogeneity on fracture, at both local and global scales. The single cantilever beam adhesion test was used to investigate interfacial fracture between polycarbonate plates and an elastic/fragile epoxy adhesive. Two surface treatments were applied to a (given) polycarbonate plate giving zones of strong and weak adhesion parallel to the crack direction. Calculated fracture energies differed from those expected from a simple rule-of-mixtures. A perturbation method, proposed by Rice, was used and results compared with crack fronts observed in situ. The technique was applied successfully but the difference in values of stress intensity factor between the zones was found substantially different from the experimental value. In an attempt to explain discrepancies, specimens with discontinuous crack fronts (adhesive and/or plates severed along the strong/weak adhesion frontier) were tested. Good agreement was found with the rule-of-mixtures predictions raising questions about the role of crack front continuity in load transfer. 相似文献
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Dr. Tim Schleif Dr. Jörg Tatchen Julien F. Rowen Frederike Beyer Prof. Dr. Elsa Sanchez-Garcia Prof. Dr. Wolfram Sander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(46):10452-10458
The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene 2 a and 3,7-dicyano-1,5-dimethylsemibullvalene 2 b were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy-atom tunneling. The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in 2 a and 2 b , two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of 2 b in cryogenic matrices were found to be smaller than the ones of 2 a under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of 2 b compared to that of 2 a results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment; however, for 2 a in a qualitatively different way than for 2 b . 相似文献
117.
The research on the electrodes of Li-ion batteries aims to increase the energy density and the power density, improve the calendar and the cycling life, without sacrificing the safety issues. A constant progress through the years has been obtained owing to the surface treatment of the particles, in particular the coating of the particles with a layer that protects the core region from side reactions with the electrolyte, prevents the loss of oxygen, and the dissolution of the metal ions in the electrolyte, or simply improve the conductivity of the powder. The purpose of the present work is to review the different surface modifications that have been tried in the past for the different electrodes that are currently commercialized, or considered as promising, including the three families of positive electrodes (lamellar, spinel, and olivine families) and the three negative electrodes (carbon, Li4Ti5O12, and silicon). The role of the different coats used to improve either the surface conductivity, or the thermal stability, or the structural integrity is discussed. The limits in the efficiency of these different coats are also analyzed along with the understanding of the surface modifications that have been proposed. 相似文献
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