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Dr. Zhoulong Fan Katherine L. Bay Dr. Xiangyang Chen Zhe Zhuang Han Seul Park Dr. Kap-Sun Yeung Prof. Dr. K. N. Houk Prof. Dr. Jin-Quan Yu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4800-4807
A simple and efficient nitrile-directed meta-C−H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U-shaped template to achieve a molecular U-turn and assemble the large-sized cyclophane transition state for the remote C−H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta-C−H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta-selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand-containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta-selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non-directed meta-C−H activation. Substituted 2-pyridone ligands were found to be key in assisting the cleavage of the meta-C−H bond in the concerted metalation–deprotonation (CMD) process. 相似文献
3.
Alain Bachelot Eric Darrigrand Katherine Mer-Nkonga 《Comptes Rendus Mathematique》2003,336(6):505-510
The aim of this work is to propose an accurate and efficient numerical approximation for high frequency diffraction of electromagnetic waves. In the context of the boundary integral equations presented in F. Collino and B. Després, to be published in J. Comput. Appl. Math., the strategy we propose combines the microlocal discretization (T. Abboud et al., in: Third International Conference on Mathematical Aspects of Wave Propagation Phenomena, SIAM, 1995, pp. 178–187) and the multilevel fast multipole method (J.M. Song, W.C. Chew, Microw. Opt. Tech. Lett. 10 (1) (1995) 14–19). This leads to a numerical method with a reduced complexity, of order O(N4/3ln(N)+NiterN2/3), instead of the complexity O(NiterN2) for a classical numerical iterative solution of integral equations. Computations on an academic geometry show that the new method improves the efficiency, for a solution with a good level of accuracy. To cite this article: A. Bachelot et al., C. R. Acad. Sci. Paris, Ser. I 336 (2003). 相似文献
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Juan A. Barceló Jonathan Bennett Alberto Ruiz 《Journal of Fourier Analysis and Applications》2003,9(6):541-562
We study the continuity properties of a projection derived from a recent characterization of Herglotz Wave Functions in the plane. Herglotz Wave Functions are the entire solutions of the Helmholtz equation which have L2-Far-Field-Pattern. The behavior of this projection is reminiscent of the Disc Multiplier Operator on both Lp and mixed Lp-normed spaces. In particular a Kakeya type set plays a central role in our analysis. As a consequence we answer a question posed by Alvarez, Folch-Gabayet and Pérez-Esteva. 相似文献
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Mary E. Neubert DAVID G. ABDALLAH Jr Sandra S. Keast Julie M. Kim Soonnam Lee Ryan M. Stayshich Margaret E. Walsh Rolfe G. Petschek Shin-Tson Wu 《Liquid crystals》2003,30(6):711-731
New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1-4; and X = C n H 2n + 1 , F, CF 3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF 3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices.
Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature. 相似文献
Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature. 相似文献
8.
Mary Beth Walsh Connie M. Moss Benny G. Johnson Dale A. Holder Jeffry D. Madura 《The Chemical Educator》2002,7(6):379-383
The need for improved interactive tutoring capabilities in educational software for chemistry problem solving is an important one clearly articulated by teachers and students. To deliver the next generation of individualized interactive capabilities users demand, it is necessary to go beyond the conventional computer-assisted instruction methodology. The focus of this paper is the assessment with first-semester general chemistry students of a recently developed artificial intelligence (AI) tutor for balancing chemical equations. This is the first such assessment of an AI-based learning tool in chemistry. Students in CHEM 121 in the Fall 2001 semester at Duquesne University (N = 273) participated in the study. Students were divided into a test group that used the AI tutor as part of their study activities and a control group that did not use the tutor. It was found that the tutor improved the performance of the test group students to a statistically significant degree, helping the weakest students the most. This study establishes the feasibility of an AI-based approach to creating advanced new tutoring software for chemistry problem solving. Access to a Web-based demonstration of the equation-balancing tutor may be obtained by emailing the corresponding author. 相似文献
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We consider a new method for producing intensity stabilization of cw lasers. This method incorporates negative feedback from a nonlinear saturable absorber to provide wideband noise-reduction and may produce an output beam for which shot noise is below the quantum limit. This new method can be used with a large variety of cw lasers and is particularly applicable to frequency-stabilized lasers which are locked to absorption lines.Permanent address: Institute of Laser Physics, Novosibirsk 630090, Russia 相似文献