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Boris A. Trofimov Tatyana E. Glotova Marina Yu. Dvorko Igor’ A. Ushakov Elena Yu. Schmidt Al’bina I. Mikhaleva 《Tetrahedron》2010,66(38):7527-3421
Triphenylphosphine catalyzes the regio- and stereospecific addition of ketoximes to acylacetylenes, whereas classical conditions using acetylene (KOH/DMSO, 70 °C) are unsuitable for this purpose. The reaction proceeds under mild conditions (CH2Cl2, rt, 7 h) to afford (E)-(O)-2-(acyl)vinylketoximes (92-98% stereoselectivity) in a yield of up to 85%. The (E)-adducts obtained are energetically less favorable than the corresponding (Z)-isomers and are gradually enriched with (Z)-isomers, thus indicating the kinetic control of (E)-stereoselectivity of the reaction. 相似文献
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Spike train regularity of the noisy neural auditory system model under the influence of two sinusoidal signals with different frequencies is investigated. For the increasing ratio m/n of the input signal frequencies (m, n are natural numbers) the linear growth of the regularity is found at the fixed difference (m - n). It is shown that the spike train regularity in the model is high for harmonious chords of input tones and low for dissonant ones. 相似文献
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Toriyama T Nakao A Yamaki Y Nakao H Murakami Y Hasegawa K Isobe M Ueda Y Ushakov AV Khomskii DI Streltsov SV Konishi T Ohta Y 《Physical review letters》2011,107(26):266402
Synchrotron x-ray diffraction experiment shows that the metal-insulator transition occurring in a ferromagnetic state of a hollandite K(2)Cr(8)O(16) is accompanied by a structural distortion from the tetragonal I4/m to monoclinic P112(1)/a phase with a √2×√2×1 supercell. Detailed electronic structure calculations demonstrate that the metal-insulator transition is caused by a Peierls instability in the quasi-one-dimensional column structure made of four coupled Cr-O chains running in the c direction, leading to the formation of tetramers of Cr ions below the transition temperature. This provides a rare example of the Peierls transition of fully spin-polarized electron systems. 相似文献
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Alexander Yu. Rulev Igor A. Ushakov Evgeniy V. Kondrashov Vasiliy M. Muzalevskiy Aleksey V. Shastin Valentine G. Nenajdenko 《Journal of fluorine chemistry》2011,132(11):945-950
The key steps of the reactions of nitrogen nucleophiles with β-halogen-β-trifluoromethylstyrenes have been studied by 19F and 1H NMR monitoring and quantum-chemical calculations. In contrast to the mechanism proposed earlier for nucleophilic vinylic substitution of captodative carbonyl-bearing haloalkenes, this reaction proceeds via either E–Ad or Ad–E sequence depending on the nature of aromatic substituents of the parent styrenes. 相似文献
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Andrei V. Afonin Dmitry V. Pavlov Igor A. Ushakov Natalia A. Keiko 《Magnetic resonance in chemistry : MRC》2012,50(7):502-510
In the 13C NMR spectra of methylglyoxal bisdimethylhydrazone, the 13C‐5 signal is shifted to higher frequencies, while the 13C‐6 signal is shifted to lower frequencies on going from the EE to ZE isomer following the trend found previously. Surprisingly, the 1H‐6 chemical shift and 1J(C‐6,H‐6) coupling constant are noticeably larger in the ZE isomer than in the EE isomer, although the configuration around the –CH═N– bond does not change. This paradox can be rationalized by the C–H?N intramolecular hydrogen bond in the ZE isomer, which is found from the quantum‐chemical calculations including Bader's quantum theory of atoms in molecules analysis. This hydrogen bond results in the increase of δ(1H‐6) and 1J(C‐6,H‐6) parameters. The effect of the C–H?N hydrogen bond on the 1H shielding and one‐bond 13C–1H coupling complicates the configurational assignment of the considered compound because of these spectral parameters. The 1H, 13C and 15N chemical shifts of the 2‐ and 8‐(CH3)2N groups attached to the –C(CH3)═N– and –CH═N– moieties, respectively, reveal pronounced difference. The ab initio calculations show that the 8‐(CH3)2N group conjugate effectively with the π‐framework, and the 2‐(CH3)2N group twisted out from the plane of the backbone and loses conjugation. As a result, the degree of charge transfer from the N‐2– and N‐8– nitrogen lone pairs to the π‐framework varies, which affects the 1H, 13C and 15N shieldings. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
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