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Palladium‐Catalyzed Regioselective C‐Benzylation via a Rearrangement Reaction: Access to Benzyl‐Substituted Anilines 下载免费PDF全文
Dr. Manuel Amézquita‐Valencia Prof. Howard Alper 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16774-16778
An unprecedented C‐benzylation rearrangement reaction, catalyzed by palladium, is reported. The reaction proceeds by rearrangement leading to the direct synthesis of para or ortho benzyl‐substituted N‐methylanilines. The product is obtained in high regioselectivity, without the need to use a ligand for the catalytic process. 相似文献
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Anna Doppler Leo D.M. Nicholls Christopher Golz Manuel Alcarazo Michael John 《Magnetic resonance in chemistry : MRC》2019,57(11):961-967
Two functionalized [6]carbohelicenes, one of which was also available in its two enantiomeric pure forms, were oriented in stretched polystyrene in CDCl3, and in a recently introduced chiral thermoresponsive lyotropic polyaspartate (poly(benzyl)0.5(phenethyl)0.5-L-aspartate) in C2D2Cl4. From the resulting 1H,13C residual dipolar couplings, the helical pitch of a methylated [6]carbohelicene was determined and found to be in agreement with theoretical predictions and existing crystal structures (d(C2,C2′) ≈ 4.3 Å). For a second [6]carbohelicene with para-methoxyphenyl substituents, a clear conformational preference of the substituents was observed. The orientational properties of the two helicene enantiomers in the chiral polyaspartate are very similar, but both drastically change around 306 K. We suggest this behavior is due to an unusual phase transition in the liquid crystal. 相似文献
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Dr. Lorena García-Hevia Dr. Manuel Bañobre-López Dr. Juan Gallo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):431-441
Manganese-based nanostructured contrast agents (CAs) entered the field of medical diagnosis through magnetic resonance imaging (MRI) some years ago. Although some of these Mn-based CAs behave as classic T1 contrast enhancers in the same way as clinical Gd-based molecules do, a new type of Mn nanomaterials have been developed to improve MRI sensitivity and potentially gather new functional information from tissues by using traditional T1 contrast enhanced MRI. These nanomaterials have been designed to respond to biological environments, mainly to pH and redox potential variations. In many cases, the differences in signal generation in these responsive Mn-based nanostructures come from intrinsic changes in the magnetic properties of Mn cations depending on their oxidation state. In other cases, no changes in the nature of Mn take place, but rather the nanomaterial as a whole responds to the change in the environment through different mechanisms, including changes in integrity and hydration state. This review focusses on the chemistry and MR performance of these responsive Mn-based nanomaterials. 相似文献
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Dr. Julia Stroh Torvid Feiler Dr. Naveed Zafar Ali Prof. Manuel E. Minas da Piedade Dr. Franziska Emmerling 《ChemistryOpen》2019,8(7):1012-1019
Mechanochemistry offers an environmentally benign and facile synthesis method for a variety of cement paste constituents. In addition, these methods can be used to selectively tune the properties of cement components. The mineral ettringite is an important component of cementitious materials and has additional technological potential due to its ion exchange properties. Synthesis of ettringite via mechanochemistry is an environmentally friendly alternative to conventional wet-chemical synthesis established in industry. This contribution explores the mechanism of a two-step mechanochemical synthesis of ettringite, which was previously found to greatly improve the reaction conversion as compared with one-pot synthesis. The crystallinity of Al(OH)3 was found to decrease during the first stage of this mechanochemical synthesis. This was correlated to a significant decrease in the particle size of Al(OH)3 in this stage. No other significant changes were found for the other components, suggesting that mechanochemical activation of Al(OH)3 is responsible for the enhanced formation of ettringite by the two-step approach. The environmentally friendly approach developed for ettringite synthesis offers a versatile synthetic strategy, which can be applied to synthesise further cementitious materials. 相似文献
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Alberto Fernández-Alarcón Dr. José Manuel Guevara-Vela José Luis Casals-Sainz Dr. Aurora Costales Dr. Evelio Francisco Dr. Ángel Martín Pendás Dr. Tomás Rocha Rinza 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(71):17035-17045
The development of chemical intuition in photochemistry faces several difficulties that result from the inadequacy of the one-particle picture, the Born–Oppenheimer approximation, and other basic ideas used to build models. It is shown herein how real-space approaches can be efficiently used to gain valuable insights in photochemistry through a simple example of red and blue shift effects: the double hypso- and bathochromic shifts in the low-lying valence excited states of (H2O)2. It is demonstrated that 1) the use of these techniques allows the perturbative language used in the theory of intermolecular interactions, even in the strongly interacting short-range regime, to be maintained; 2) one and only one molecule is photoexcited in each of the addressed excited states and 3) the electrostatic interaction between the in-the-cluster molecular dipoles provides a fairly intuitive rationalisation of the observed batho- and hypsochromism. The methods exploited and illustrated herein are able to maintain the individuality and properties of the interacting entities in a molecular aggregate, and thereby they allow chemical intuition in general states, at any geometry and using a broad variety of electronic structure methods to be kept and built. 相似文献