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Dr. Suhua Li Ru‐Yi Zhu Dr. Kai‐Jiong Xiao Prof. Dr. Jin‐Quan Yu 《Angewandte Chemie (International ed. in English)》2016,55(13):4317-4321
PdII‐catalyzed arylation of γ‐C(sp3)?H bonds of aliphatic acid‐derived amides was developed by using quinoline‐based ligands. Various γ‐aryl‐α‐amino acids were prepared from natural amino acids using this method. The influence of ligand structure on reactivity was also systematically investigated. 相似文献
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The rates of aqua substitution from [Pt{2-(pyrazol-1-ylmethyl)quinoline}(H2O)2](ClO4)2, [Pt(H2Qn)], [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)quinoline}(H2O)2](ClO4)2, [Pt(dCH3Qn)], [Pt{2-[(3,5-bis(trifluoromethyl)pyrazol-1-ylmethyl]quinoline}(H2O)2](ClO4)2, [Pt(dCF3Qn)], and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazol-1-ylmethyl]pyridine}(H2O)2](ClO4)2, [Pt(dCF3Py)], with three sulfur donor nucleophiles were studied. The reactions were followed under pseudo-first-order conditions as a function of nucleophile concentration and temperature using a stopped-flow analyzer and UV/visible spectrophotometry. The substitution reactions proceeded sequentially. The second-order rate constants for substituting the aqua ligands in the first substitution step increased in the order Pt(dCH3Qn) < Pt(dCF3Qn) < Pt(H2Qn) < Pt(dCF3Py), while that of the second substitution step was Pt(dCH3Qn) < Pt(dCF3Qn) < Pt(dCF3Py) < Pt(H2Qn). The reactivity trends confirm that the quinoline substructure in the (pyrazolylmethyl)quinoline ligands acts as an apparent donor of electron density toward the metal center rather than being a π-acceptor. Measured pKa values from spectrophotometric acid–base titrations were Pt(H2Qn) (pKa1 = 4.56; pKa2 = 6.32), Pt(dCH3Qn) (pKa1 = 4.88; pKa2 = 6.31), Pt(dCF3Qn) (pKa1 = 4.07; pKa2 = 6.35), and Pt(dCF3Py) (pKa1 = 4.76; pKa2 = 6.27). The activation parameters from the temperature dependence of the second-order rate constants support an associative mechanism of substitution. 相似文献
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Synthesis of Furano[3,2-c]- and Pyrano[3,2-c]quinolines upon Imino Diels-Alder Reactions Initiated by Nitrosonium (NO^+) 总被引:1,自引:0,他引:1
Efficient nitrosonium (NO+)-initiated aza-Diels-Alder reactions of N-arylimines with 2,3-dihydrofuran or 3,4-dihydro-2H-pyran allowed access to furano[3,2-c]- or pyrano[3,2-c]quinolines. A mixture of cis and trans-quinoline isomers was obtained in various ratios and yields. 相似文献
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E. V. Trofimova A. N. Fedotov S. S. Mochalov Yu. S. Shabarov N. S. Zefirov 《ChemInform》2001,32(29):148-148
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