直链淀粉三(3,5-二甲基苯基)氨基甲酸酯手性鉴别的机理。

Enantiomer Pub Date : 2002-11-01 DOI:10.1080/10242430215711
Y Bereznitski, R LoBrutto, N Variankaval, R Thompson, K Thompson, P Sajonz, L S Crocker, J Kowal, D Cai, M Journet, T Wang, J Wyvratt, N Grinberg
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引用次数: 23

摘要

[2R-[2 α (R*),3 α]]-5-[[2-[1-[3,5-二-(三氟甲基)苯基]乙氧基]-3(S)-4-氟苯基)4-morpholinyl]-甲基]- n, n -二甲基- 1h -1,2,3-三唑-4-甲烷胺盐酸盐在直链三-3,5-二甲基苯基氨基甲酸酯固定相上分离。对映体的保留主要是由弱氢键控制的,而对映体的选择性是由其他类型的相互作用控制的,例如,在氨基甲酸酯直链中的包合。1 α与温度倒数的Van't hoffplot是非线性的,可以分为两个线性区域。一个区域处于低温(5℃-约20℃),另一个区域处于25℃-70℃之间,斜率变化发生在16℃至20℃之间。DSC实验表明,这种行为可归因于氢键断裂引发构象变化。分子模拟表明,相互作用能与实验得到的洗脱顺序之间存在相关性。保留最多的对映体(R,R, s -对映体)通过三唑质子与固定相的C=O基团之间的氢键以及固定相间隙中的包合物与固定相相互作用。另一个对映体在三唑质子和固定相的C=O基团之间有一个分叉的氢键,导致一个不太稳定的配合物。
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Mechanistic aspects of chiral discrimination on an amylose tris(3,5-dimethylphenyl)carbamate.

The separation of [2R-[2alpha(R*),3alpha]]-5-[[2-[1-[3,5-bis-(trifluoromethyl)phenyl]ethoxy]-3(S)-4-fluorophenyl)4-morpholinyl]-methyl]-N,N-dimethyl-1H-1,2,3-triazole-4-methanamine hydrochloride from its enantiomer was achieved on an amylose tris-3,5-dimethylphenyl carbamate stationary phase. The retention of the enantiomers is dominated by weak hydrogen bonds while the enantioselectivity is governed by other kinds of interactions, e.g., inclusion in the amylose carbamate chains. Van't Hoffplots of 1nalpha vs. reciprocal temperature were non-linear and could be divided into two linear regions. One region at low temperature (5 degrees C- approximately 20 degrees C) and another one between 25 degrees C-70 degrees C with the change in slope occurring between 16 degrees C and 20 degrees C. DSC experiments suggested that the behavior can be attributed to breakage of H-bonds triggering a conformational change. Molecular simulation indicated a correlation between the interaction energies and the elution order obtained experimentally. The most retained enantiomer (R,R,S-enantiomer) interacts with the stationary phase through a hydrogen bond between the triazole proton and the C=O groups of the stationary phase, as well as through an inclusion in the cleft of the stationary phase. The other enantiomer exhibits a bifurcated H-bond between the triazolic proton and the C=O groups of the stationary phase leading to a less stable complex.

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