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31.
Readily Accessible Bulky Iron Catalysts exhibiting Site Selectivity in the Oxidation of Steroidal Substrates 下载免费PDF全文
Dr. David Font Dr. Mercè Canta Michela Milan Olaf Cussó Dr. Xavi Ribas Dr. Robertus J. M. Klein Gebbink Dr. Miquel Costas 《Angewandte Chemie (International ed. in English)》2016,55(19):5776-5779
Bulky iron complexes are described that catalyze the site‐selective oxidation of alkyl C?H bonds with hydrogen peroxide under mild conditions. Steric bulk at the iron center is introduced by appending trialkylsilyl groups at the meta‐position of the pyridines in tetradentate aminopyridine ligands, and this effect translates into high product yields, an enhanced preferential oxidation of secondary over tertiary C?H bonds, and the ability to perform site‐selective oxidation of methylenic sites in terpenoid and steroidal substrates. Unprecedented site selective oxidation at C6 and C12 methylenic sites in steroidal substrates is shown to be governed by the chirality of the catalysts. 相似文献
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Mercè Arasa Xavier Ramis Josep Maria Salla Ana Mantecón Angels Serra 《Journal of polymer science. Part A, Polymer chemistry》2007,45(11):2129-2141
Mixtures of DGEBA with γ-valerolactone (γ-VL) or α-methyl-γ-butyrolactone (γ-MBL) 2:1 (mol/mol) were cationically copolymerized in the presence of scandium, ytterbium, or lanthanum triflates as initiators. The evolution of the different reactive groups was followed by means of FTIR/ATR spectroscopy. From these experiments, we could detect the coexistence of two unexpected processes: a reversion of the intermediate spiroorthoester formed to the initial products and a depolymerization process, which only takes place in samples with γ-VL, when scandium triflate was used as initiator or when the proportion of ytterbium triflate was increased from 1 to 3 phr. When γ-MBL was used as comonomer no depolymerization occurs which supports the proposed mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2129–2141, 2007 相似文献
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Albert J Cadena JM González A Granell J Solans X Font-Bardia M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(3):887-894
We report that the action of Lewis bases, such as triphenylphosphine, pyridine, or trimethylamine, on imine metallacycles derived from amino acids leads to the formation of the first organometallic compound of an NH aldimine, a highly reactive organic species, and the corresponding alpha-ketoester, in a deamination reaction that mimics the metabolism of alpha-amino acids. The synthesis of different cyclopalladated compounds by a reaction between palladium acetate and the Schiff bases 2,4,6-Me(3)C(6)H(2)CH=NCH(R(1))COOR(2) (R(1) = CH(2)Ph, R(2) = Et and R(1) = Ph, R(2) = Me) is also reported. 相似文献
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Capapé A Crespo M Granell J Vizcarro A Zafrilla J Font-Bardía M Solans X 《Chemical communications (Cambridge, England)》2006,(39):4128-4130
A novel platinum-mediated process involving intermolecular activation of a C(aryl)-H bond of toluene, intramolecular activation of an imine C(aryl)-Cl bond and formation of a C-C bond is reported. 相似文献
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Saul F. Teloxa Stuart C. D. Kennington Marc Camats Prof. Pedro Romea Prof. Fèlix Urpí Prof. Gabriel Aullón Dr. Mercè Font-Bardia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(50):11540-11548
A direct and highly enantioselective reaction of N-azidoacetyl-1,3-thiazolidine-2-thione with trimethyl orthoformate catalyzed by Tol-BINAPNiCl2 in the presence of TESOTf and 2,6-lutidine is reported. The heterocyclic scaffold can be easily removed by addition of a wide array of amines to give the corresponding enantiomerically pure 2-azido-3,3-dimethoxypropanamides in high yields. Appropriate manipulation of the N-benzyl amide derivative provides an efficient access to the antiepileptic agent lacosamide through a new enantioselective C−C bond-forming process. DFT computational studies uncover clues for the understanding of the remarkable stereocontrol of the addition of a nickel(II) enolate to a putative oxocarbenium intermediate from trimethyl orthoformate. 相似文献
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Deumal M Bearpark MJ Robb MA Pontillon Y Novoa JJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6422-6432
The mechanism of magnetic interactions in the bulk ferromagnet para-(methylthio)phenyl nitronyl nitroxide crystal (YUJNEW) has been theoretically reinvestigated, using only data from ab initio calculations and avoiding any a priori assumptions. We first calculate the microscopic magnetic interactions (JAB exchange couplings) between all unique radical pairs in the crystal, and then generate the macroscopic magnetic properties from the energy levels of the corresponding Heisenberg Hamiltonian. We thus propose a first principles, bottom-up (i.e. micro-to-macro) approach that brings theory and experiment together. We have applied this strategy to study the magnetism of YUJNEW using data from the previously reported 298 and 114 K crystal structures, and also data from a 10 K neutron diffraction structure fully reported in this work. The magnetic topology at 298 K is two-dimensional: noninteracting planes, with three different in-plane JAB pair interactions (+0.24, +0.09, and -0.11 cm(-1)) and one numerically negligible (+0.02 cm(-1)) inter-plane JAB interaction. In contrast, the magnetic topology at 114 and 10 K is three-dimensional, with two non-negligible in-plane JAB constants (+0.11 and +0.07 cm(-1) at 114 K; +0.22 and +0.07 cm(-1) at 10 K) and one inter-plane pair interaction (+0.07 cm(-1) at 114 K; +0.08 cm(-1) at 10 K). Although this three-dimensional magnetic topology is consistent with YUJNEW being a bulk ferromagnet, there is only a qualitative agreement between computed and experimental magnetic susceptibility chiT(T) data at 114 K. However, the experimental chiT(T) curve is quantitatively reproduced at 10 K. The heat capacity curve presents a peak at around 0.12 K, close to the estimated experimental peak (0.20 K). 相似文献
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Larrosa I Romea P Urpí F Balsells D Vilarrasa J Font-Bardia M Solans X 《Organic letters》2002,4(26):4651-4654
[reaction: see text] Lewis acid mediated addition of chiral titanium enolates to glycals provides either alpha- or beta-1'-methyl-substituted C-glycosides. This highly stereoselective methodology permits the modular preparation of three of the four possible diastereomers. 相似文献
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Dimerization of Pyramidalized 3,4,8,9‐Tetramethyltetracyclo [4.4.0.03,9.04,8]dec‐1(6)‐ene to a Hydrocarbon Featuring Four Cyclohexane Rings in Boat Conformations 下载免费PDF全文
Matias Rey‐Carrizo Marta Barniol‐Xicota Dr. Mercè Font‐Bardia Prof. Dr. Santiago Vázquez 《Angewandte Chemie (International ed. in English)》2014,53(31):8195-8199
The synthesis, chemical trapping, and dimerization of a highly pyramidalized alkene is reported. Its dimer is a unique nonacycle featuring three planar cyclobutane rings, four cyclopentane rings, and four cyclohexane rings in boat conformations. The X‐ray diffraction analysis showed a H–H distance between the flagpole hydrogen atoms of 1.999 Å and a separation of 2.619 Å between the two flagpole carbon atoms. The three cyclobutane rings of the dimer were thermally stable. 相似文献