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41.
Tian SX 《The Journal of chemical physics》2005,123(24):244310
The low-lying conformers of N-/O-methylglycine are studied by ab initio calculations at the B3LYP, MP3, and MP4(SDQ) levels of theory with the aug-cc-pVDZ basis set. The conformers having the intramolecular hydrogen bonds N-H...O=C or O-H...N are more stable than the others. Vertical ionization energies for the valence molecular orbitals of each conformer predicted with the electron propagator theory in the partial third-order quasiparticle approximation are in good agreement with the experimental data available in the literatures. The relative energies of the conformers and comparison between the simulated and the experimental photoelectron spectra demonstrate that there are at least three and two conformers of N- and O-methylglycine, respectively, in the gas-phase experiments. The intramolecular hydrogen bonding O-H...N effects on the molecular electronic structures are discussed for the glycine methyl derivatives, on the basis of the ab initio electronic structure calculations, natural orbital bond, and atoms-in-molecules analyses. The intramolecular hydrogen bonding O-H...N interactions hardly affect the electronic structures of the O-NH2-CH2-C(=O)-O-CH3 and alpha-methylated NH2-CH2-C(CH3)OOH conformers, while the similar intramolecular interactions lead to the significantly lower-energy levels of the highest occupied molecular orbitals for the N-(CH3-NH-CH2-COOH) and beta-methylated (NH2-CH2-CH2-COOH) conformers. 相似文献
42.
Gaul C Njardarson JT Shan D Dorn DC Wu KD Tong WP Huang XY Moore MA Danishefsky SJ 《Journal of the American Chemical Society》2004,126(36):11326-11337
The first asymmetric total synthesis of (+)-migrastatin (1), a macrolide natural product with anti-metastatic properties, has been accomplished. Our concise and flexible approach utilized a Lewis acid-catalyzed diene aldehyde condensation (LACDAC) to install the three contiguous stereocenters and the trisubstituted (Z)-alkene of migrastatin (2 + 3 --> 21). Construction of the two remaining stereocenters and incorporation of the glutarimide-containing side chain was achieved by an anti-selective aldol addition of propionyl oxazolidinone 28 to angelic aldehyde 27, followed by a Horner-Wadsworth-Emmons (HWE) coupling of 32 with glutarimide aldehyde 5. Finally, the assembly of the macrocycle was realized by a highly (E)-selective ring-closing metathesis (35 --> 37). Utilizing the power of diverted total synthesis (DTS), a series of otherwise inaccessible analogues was prepared and evaluated for their potential as tumor cell migration inhibitors in several in vitro assays. These studies revealed a dramatic increase in activity when the natural motif was considerably simplified, presenting macrolactones 45 and 48, as well as macrolactam 55, macroketone 60, and CF(3)-alcohol 71 as promising anti-metastatic agents. 相似文献
43.
The B3LYP and MP2 methods with 6-31G* basis set were used to predict the geometries of N, N-dimethylformamide (DMF) dimer and DMF–aromatic hydrocarbons interaction systems. A total of 10 conformers were obtained with
no imaginary frequencies, respectively. The interaction energies of these binary mixtures have been obtained. The analyses
of chelpg charge distribution and the atoms in molecules theory (AIM) were used to analyze the nature of the interaction.
The results show the presence of hydrogen bonds between DMF and aromatic hydrocarbons. The interaction between DMF and benzonitrile
is the strongest with the interaction energy of −21.58 kJ mol−1 (BSSE corrected), and the intensity order of interactions is DMF–benzonitrile: d2 > DMF–DMF: a2 > DMF–toluene: c1 > DMF–benzene:
b2. 相似文献
44.
IntroductionItiswellknownthatyttriumcanbeusedinmanyfields ,suchasmetallurgy ,ceramics ,lasersandelectron ics ,especiallyinfluorescentmaterialswhoseneedforhighpurityyttriumoxideisincreasing .InChina ,there sourceofyttriumisrich ,andthehighpureyttriumisbe ingo… 相似文献
45.
46.
Promotion of Ionic Liquid to Dimethyl Carbonate Synthesis from Methanol and Carbcn Dioxide 总被引:2,自引:0,他引:2
Promotion of ionic liquid, 1-ethyl-3-methylimidazolium bromide (emimBr), to the synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in the presence of potassium carbonate and less amount of methyl iodide under mild conditions was investigated. The results showed that the high selectivity and raised yield of DMC was achieved due to the addition of emimBr in the reaction system. And effect of several reaction conditions such as temperature, pressure and amount of emimBr was discussed. 相似文献
47.
48.
49.
Two new C18-norditerpenoid alkaloids from Aconitum delavayi 总被引:2,自引:0,他引:2
Shan Hao Jiang Hai Qing Wang Yi Ming Li Shuang Jun Lin Jun Jie Tan Da Yuan Zhu 《中国化学快报》2007,18(4):409-411
Further phytochemical investigation of the unique C18-norditerpenoid alkaloids from the roots of Aconitum delavayi Franch ledto the isolation of two new norditerpenoid alkaloids,delavaconitine F 1 and delavaconitine G 2.Their structures were determinedfrom spectroscopic evidence. 相似文献
50.
A series of 1,4‐diarylquinoline derivatives were synthesized by the reaction of arylmethylidenemalononitriles or 2‐cyano‐3‐aryl‐1‐acrylate and 3‐arylamino‐5,5‐dimethylcyclohex‐2‐enone in aqueous media at 100 °C catalyzed by TEBAC. Meanwhile, the water medium was chosen as green solvent. 相似文献