• 제목/요약/키워드: Ketimine

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M.O. Studies of Configuration and Conformation (Part II) Configuration and Conformation of Ketimine isomers

  • Kim, Shi-Choon;Chun, Young-Gu;Lee, Ikchoon
    • Nuclear Engineering and Technology
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    • 제9권1호
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    • pp.39-44
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    • 1977
  • N-methyl-C-phenylalkyl ketimine 이성질체, Ph-CR=N$CH_3$ (R=H, $CH_3$, $CH_3$CH$_2$)의 배치와 형태를 EHT 분자궤도함수법으로 연구하였다. 계산결과는 C=N 이중결함에 대하여 E-형의 배치가 Z-형의 배치보다 안전함을 나타내고 있다. N-methyl-C-phenylaldimine과 N-methyl-C-phenylmethylketimine에서는 phenyl 고러 회전자가 C=N 평면과 동일평면에 있는 형태가 안정하다. N-methyl-C-phenylethylketimine에서는 phenyl 고리와 C=N결합이 동일평면에 있고 회전자 $CH_3$CH$_2$-가 C=N 평면과 90$^{\circ}$인 gauche형이 가장 안정하다.

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Solvent-free Microwave-Assisted Ortho-Alkylation of Aromatic Ketimine with Acrylic Acid Derivatives by Rh(I) Catalyst

  • Jo, Eun-Ae;Ahn, Jeong-Ae;Jun, Chul-Ho
    • Bulletin of the Korean Chemical Society
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    • 제28권11호
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    • pp.2020-2024
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    • 2007
  • The article reports the synthesis of a novel bispyridino-18-crown-6 ether, 7-{[(5S,15S)-5,15-diphenyl- 3,6,14,17-tetraoxa-23,24-diazatricyclo[17.3.1.18,12]tetracosa-1(23),8(24),9,11,19,21-hexaen-10-yl]oxy}heptylferrocenamide 6, bearing the C2-symmetric diphenyl substituents as chiral barriers and the ferrocenyl groups serving as an electrochemical sensor, and its electrochemical study with D- and L-AlaOMe·HCl as the guest by cyclovoltametry.

Synthesis of$\beta,\gamma$-Unsaturated Ketones through Ligand-Promoted Hydroiminoacylation of Dienes by Rh

  • Jun Chul-Ho;Koo Bon-Tak;Kang Jung-Bu;Kim Keun-Jae
    • Bulletin of the Korean Chemical Society
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    • 제15권12호
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    • pp.1064-1069
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    • 1994
  • Chlorobis(isoprene)rhodium(Ⅰ) (3), prepared by olefin-exchange reaction of chlorobis(cyclooctene)rhodium dimer (2) with isoprene, reacted with benzaldimine 4 to give iminoacylrhodium(Ⅲ) ${\eta}^3$-1,2-dimethylallyl complex 6. Ligand-promoted reductive elimination of 6 by pyridine and P(OMe)$_3$ produced ${\beta},{\gamma}$-unsaturated ketimine 8, which was readily hydrolyzed to give ${\beta},{\gamma}$-unsaturated ketone 9. Other methyl branched dienes such as 2,3-dimethylbutadiene, 3-methyl-1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3-methyl-1,4-pentadiene and 2-methyl-1,4-pentadiene, were applied the synthesis of ${\beta},{\gamma}$-unsaturated ketones. In case of 2,4-dimethyl-1,3-pentadiene, only ${\gamma},{\delta}$ -unsaturated ketone 25, 1,2-addition product, was obtained, may be due to the mono-olefin coordination.

Effects of Salts on the Conformation and Catalytic Properties of D-Amino Acid Aminotransferase

  • Ro, Hyeon-Su
    • BMB Reports
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    • 제35권3호
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    • pp.306-312
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    • 2002
  • The effects of salts on the biochemical properties of D-amino acid aminotransferase from Bacillus sp. YM-1 have been studied to elucidate both the inhibitory effects of salts on the activity and the protective effects of salts on the substrate-induced inactivation. The results from UV-visible spectroscopy studies on the reaction of the enzyme with D-serine revealed that salt significantly reduced the rate of the formation of the quinonoid intermediate and its accumulation. The kinetic and spectroscopy studies of the reaction with $\alpha$-[$^2H$]-DL-serine in different concentrations of NaCl provided evidence that the rate-limiting step was changed from the deprotonation of the external aldimine to another step(s), presumably to the hydrolysis of the ketimine. Gel filtration chromatography data in the presence of NaCl showed that the enzyme volume was reduced sharply with the increasing NaCl concentration, up to 100 mM. An additional increase of the NaCl concentration did not affect the elution volume, which suggests that the enzyme has a limited number of salt-binding groups. These results provide detailed mechanistic evidence for the way salts inhibit the catalytic activity of D-amino acid aminotransferase.