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11.
Ugo Authesserre Sophie Hameury Aymeric Dajnak Nathalie Saffon-Merceron Antoine Baceiredo David Madec Eddy Maerten 《Molecules (Basel, Switzerland)》2021,26(7)
Due to their remarkable electronic features, recent years have witnessed the emergence of carbones L2C, which consist in two donating L ligands coordinating a central carbon atom bearing two lone pairs. In this context, the phosphine/sulfoxide-supported carbone 4 exhibits a strong nucleophilic character, and here, we describe its ability to coordinate dichlorogermylene. Two original stable coordination complexes were obtained and fully characterized in solution and in the solid state by NMR spectroscopy and X-ray diffraction analysis, respectively. At 60 °C, in the presence of 4, the Ge(II)-complex 5 undergoes a slow isomerization that transforms the bis-ylide ligand into an yldiide. 相似文献
12.
Dr. Florie Lavigne Dr. Eddy Maerten Dr. Gilles Alcaraz Dr. Nathalie Saffon‐Merceron Dr. Antoine Baceiredo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):297-303
We recently disclosed the synthesis of a novel “push–pull” boryl(phosphino)carbene. To determine the influence of this substitution pattern on the chemical behaviour, a study into the reactivity of the prototype ( 1 ) of this new family of B(sp2)‐substituted phosphinocarbenes was undertaken. Carbene 1 exhibits one of the most common intramolecular rearrangements of singlet carbenes, involving a 1,2‐mesityl shift, and typical [2+1] cycloaddition reactions with electron‐poor acrylonitrile. A pronounced α,β‐ambiphilic character was also shown by the reaction of 1 with benzaldehyde, leading to phosphorylalkene 4 . Due to its specific electronic properties, carbene 1 also exhibits unprecedented reactivity with chloroacrylonitrile, enabling the formation of bicyclo[1.1.0]phosphetanium salt 6 and borylcyclopropene 9 , which have been fully characterised by NMR spectroscopy and X‐ray crystallography. 相似文献
13.
Carbon Dioxide as a Protecting Group: Highly Efficient and Selective Catalytic Access to Cyclic cis‐Diol Scaffolds
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Victor Laserna Dr. Giulia Fiorani Dr. Christopher J. Whiteoak Dr. Eddy Martin Eduardo Escudero‐Adán Prof. Dr. Arjan W. Kleij 《Angewandte Chemie (International ed. in English)》2014,53(39):10416-10419
The efficient and highly selective formation of a wide range of (hetero)cyclic cis‐diol scaffolds using aminotriphenolate‐based metal catalysts is reported. The key intermediates are cyclic carbonates, which are obtained in high yield and with high levels of diastereo‐ and chemoselectivity from the parent oxirane precursors and carbon dioxide. Deprotection of the carbonate structures affords synthetically useful cis‐diol scaffolds with different ring sizes that incorporate various functional groups. This atom‐efficient method allows the simple construction of diol synthons using inexpensive and accessible precursors and green metal catalysts and showcases the use of CO2 as a temporary protecting group. 相似文献
14.
Willem Jespers Dr. Grégory Verdon Dr. Jhonny Azuaje Dr. Maria Majellaro Dr. Henrik Keränen Prof. Xerardo García-Mera Dr. Miles Congreve Dr. Francesca Deflorian Dr. Chris de Graaf Dr. Andrei Zhukov Dr. Andrew S. Doré Dr. Jonathan S. Mason Prof. Johan Åqvist Dr. Robert M. Cooke Prof. Eddy Sotelo Dr. Hugo Gutiérrez-de-Terán 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(38):16679-16686
We present a robust protocol based on iterations of free energy perturbation (FEP) calculations, chemical synthesis, biophysical mapping and X-ray crystallography to reveal the binding mode of an antagonist series to the A2A adenosine receptor (AR). Eight A2AAR binding site mutations from biophysical mapping experiments were initially analyzed with sidechain FEP simulations, performed on alternate binding modes. The results distinctively supported one binding mode, which was subsequently used to design new chromone derivatives. Their affinities for the A2AAR were experimentally determined and investigated through a cycle of ligand-FEP calculations, validating the binding orientation of the different chemical substituents proposed. Subsequent X-ray crystallography of the A2AAR with a low and a high affinity chromone derivative confirmed the predicted binding orientation. The new molecules and structures here reported were driven by free energy calculations, and provide new insights on antagonist binding to the A2AAR, an emerging target in immuno-oncology. 相似文献
15.
Eddy Thiriot Sébastien Canneaux Eric Hénon Frédéric Bohr 《Reaction Kinetics and Catalysis Letters》2005,85(1):123-129
Summary We show the presence of an ether group in alkoxy radicals significantly lowers the activation energy of the b-C-H dissociation and only slightly increases the isomerization barrier. Moreover, an 1-6 isomerization mechanism involving a 7-membered transition state may compete with the usual 1-5 isomerization. 相似文献
16.
William F. Eddy 《Probability Theory and Related Fields》1982,59(3):279-290
Summary In a decreasing sequence of intervals centered on the true mode the normalized kernel estimate of the density converges weakly to a nonstationary Gaussian random process. The expected value of this process is a parabola through the origin. The covariance function of this process depends on the smoothness of the kernel. When the kernel is mean-square differentiable the location of the maximum of this process has a normal distribution. When the kernel is discontinuous the location of the maximum has a distribution related to a solution of the heat equation.Research supported in part by the National Science Foundation under grant MCS-78-02422 and MCS-80-05115 to Carnegie-Mellon University 相似文献
17.
T.L. Eddy C.J. Cremers H.S. Hsia 《Journal of Quantitative Spectroscopy & Radiative Transfer》1977,17(3):287-296
The continuum emission coefficient relation for a plasma in Multithermal Equilibrium (MTE) is derived using the partial-MTE ionization equation. The results are presented in a form using the nonhydrogenic free-bound Gaunt factors of Schlüter. Measurements on a 200 A, 1 atm, constricted argon arc indicate that electron densities calculated from the MTE continuum relation and Schlüter's ξfb values exceed electron densities from the Stark broadening of Hβ by 15–30%. Experimental values of ξfb are up to 3 times larger than Schlüter's values, but are in agreement with the values of Morris and Krey at 5 atm, which is probably one of the few similar experiments actually in or near complete LTE. In the present experiment at the arc axis: Ne(Hβ) = 1.00 × 1017cm-3 (±8%); Te = 34,000 K (±20%); Texa = 12,000 K (±3%); Texβ = 9000 K (±5%); and Ta = Ti = 10,000 K (±68%). The probable errors reflect the need for more accurate transition probabilities which had an uncertainty of 25%. 相似文献
18.
A series of 6-phenyl-3(2H)-pyridazinones bearing different substitution at the 5 position of the pyridazinone ring were prepared in the search for new platelet aggregation inhibitors. The structure of the final compounds was determined on the basis of spectroscopics methods. 相似文献
19.
We present a study of the Gaussian q-measure introduced by Díaz and Teruel from a probabilistic and from a combinatorial viewpoint. A main motivation for the introduction of the Gaussian q-measure is that its moments are exactly the q-analogues of the double factorial numbers. We show that the Gaussian q-measure interpolates between the uniform measure on the interval [−1,1] and the Gaussian measure on the real line. 相似文献
20.
The intermolecular clusters of sulfur dioxide with water, SO2(H2O)n (n = 2~5), are studied by using B3LYP density functional theory and MP2 ab initio methods along with the large basis sets (6-311++G(d,p) and aug-cc-pVDZ). The equilibrium geometries, intermolecular binding energies, and anharmonic frequencies of the clusters are calculated and compared with those of pure water clusters and available experiments. SO2 tends to form cyclic hydrogen-bonded complexes with two or three water molecules. In the larger clusters, however, water molecules begin to retain the structure of pure water clusters and segregate from SO2. Infrared absorption assignments for the small clusters are discussed to resolve a possible incorrect assignment in a recent spectroscopic experiment on the clusters. 相似文献