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1.
Enantioselective Organocatalytic Reduction of β‐Trifluoromethyl Nitroalkenes: An Efficient Strategy for the Synthesis of Chiral β‐Trifluoromethyl Amines 下载免费PDF全文
Elisabetta Massolo Prof. Maurizio Benaglia Manuel Orlandi Dr. Sergio Rossi Giuseppe Celentano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3589-3595
An efficient organocatalytic stereoselective reduction of β‐trifluoromethyl‐substituted nitroalkenes, mediated by 3,5‐dicarboxylic ester‐dihydropyridines (Hantzsch ester type), has been successfully developed. A multifunctional thiourea‐based (S)‐valine derivative was found to be the catalyst of choice, promoting the reaction in up to 97 % ee. The methodology has been applied to a wide variety of substrates, leading to the formation of differently substituted precursors of enantiomerically enriched β‐trifluoromethyl amines. The mechanism of the reaction and the mode of action of the metal‐free catalytic species were computationally investigated; on the basis of DFT transition‐state (TS) analysis, a model of stereoselection was also proposed. 相似文献
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Valentina Bleve Christian Schäfer Dr. Paola Franchi Dr. Serena Silvi Prof. Dr. Elisabetta Mezzina Prof. Dr. Alberto Credi Prof. Marco Lucarini 《ChemistryOpen》2015,4(1):2-21
An acid–base switchable molecular shuttle based on a [2]rotaxane, incorporating stable radical units in both the ring and dumbbell components, is reported. The [2]rotaxane comprises a dibenzo[24]crown-8 ring (DB24C8) interlocked with a dumbbell component that possesses a dialkylammonium (NH2+) and a 4,4′-bipyridinium (BPY2+) recognition site. Deprotonation of the rotaxane NH2+ centers effects a quantitative displacement of the DB24C8 macroring to the BPY2+ recognition site, a process that can be reversed by acid treatment. Interaction between stable 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radicals connected to the ring and dumbbell components could be switched between noncoupled (three-line electron paramagnetic resonance (EPR) spectrum) and coupled (five-line EPR spectrum) upon displacement of the spin-labelled DB24C8 macroring. The complete base- and acid-induced switching cycle of the EPR pattern was repeated six times without an appreciable loss of signal, highlighting the reversibility of the process. Hence, this molecular machine is capable of switching on/off magnetic interactions by chemically driven reversible mechanical effects. A system of this kind represents an initial step towards a new generation of nanoscale magnetic switches that may be of interest for a variety of applications. 相似文献
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Elisabetta Barletta Sorin Dragomir Howard Jacobowitz 《Complex Analysis and Operator Theory》2017,11(8):1685-1713
The total space \({\mathfrak M} \approx {\mathbb H}_1 \times S^1\) of the canonical circle bundle over the 3-dimensional Heisenberg group \({\mathbb H}_1\) is a space–time with the Lorentzian metric \(F_{\theta _0}\) (Fefferman’s metric) associated to the canonical Tanaka–Webster flat contact form \(\theta _0\) on \({\mathbb H}_1\). The matter and energy content of \(\mathfrak M\) is described by the energy-momentum tensor \({T}_{\mu \nu }\) (the trace-less Ricci tensor of \(F_{\theta _0}\)) as an effect of the non flat nature of Feferman’s metric \(F_{\theta _0}\). We study the gravitational field equations \(R_{\mu \nu } - (1/2) \, R \, g_{\mu \nu } = {T}_{\mu \nu }\) on \({\mathfrak M}\). We consider the first order perturbation \(g = F_{\theta _0} + \epsilon \, h\), \(\epsilon<< 1\), and linearize the field equations about \(F_{\theta _0}\). We determine a Lorentzian metric g on \({\mathfrak M}\) which solves the linearized field equations corresponding to a diagonal perturbation h. 相似文献
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Dr. Ali Munaim Yousif Stefania Colarusso Elisabetta Bianchi 《European journal of organic chemistry》2023,26(12):e202300099
Peptide drug discovery often benefits from the large structural diversity permitted by unnatural amino acids (UAAs). Indeed, numerous approved peptide drugs include UAAs in their sequences. Therefore, innovative chemical approaches either to synthesize UAAs or to allow late-stage functionalization of peptides are emerging themes in peptide drug discovery. Thanks to the recent advances in deaminative strategies using alkylpyridiniums salts, often referred to as Katritzky salts, a variety of radical alkylation methods have been developed. In recent years the use of Katritzky salts have become popular in peptide chemistry due to their ease of preparation from a primary amine, which is a predominant functional group in amino acids. This review highlights the progress that has been made by using Katritzky salts in the synthesis of UAAs, late-stage peptide functionalization, and peptide macrocyclization. 相似文献
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Elisa Musella Dr. Isacco Gualandi Dr. Erika Scavetta Dr. Massimo Gazzano Arianna Rivalta Dr. Elisabetta Venuti Dr. Meganne Christian Dr. Vittorio Morandi Prof. Dr. Domenica Tonelli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(71):16301-16310
Layered double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, the electrochemical approach does not usually allow for a fine control of the MII/MIII ratio in the synthesized material. By employing a recently proposed potentiodynamic method, LDH films of controlled composition are herein prepared with good reproducibility, using different ratios of the trivalent (Fe or Al) to bivalent (Co) cations in the electrolytic solution. All the obtained materials are shown to be effective oxygen evolution reaction (OER) catalysts, and are thoroughly characterized by a multi-technique approach, including FE-SEM, XRD, Raman, AES and a wide range of electrochemical procedures. 相似文献