含有非正规残留物替代模式的亚利法性尿素寡合体的螺旋形成倾向
Nagendar Pendem1, Céline Douat, Paul Claudon
1Université de Bordeaux -CNRS UMR 5248, CBMN, Institut Européen de Chimie et Biologie, 2 rue Robert Escarpit, 33607 Pessac, France.
Journal of the American Chemical Society
|March 1, 2013
概括
亚利法性橄树形成螺旋体,但它们的结构对残留物修饰很敏感. 研究人员探索了不同替代模式如何影响这些型模拟物中的螺旋形成.
科学领域:
- 化学生物学 化学生物学
- 有机化学 有机化学
- 聚合物科学 聚合物科学
背景情况:
- 亚利法性N,N'-结合的橄油是一种模仿折合物.
- 这些折叠体采用了明确的螺旋式二次结构.
- 螺旋稳定性由遥远的三中心键形成伪环.
研究的目的:
- 调查螺形成规则在oligoureas.
- 为了确定替代替代模式与螺旋体几何学的兼容性.
- 了解残留物变化如何影响螺旋结构,以实现潜在的功能应用.
主要方法:
- 系统地评估改性橄尿素五合体中螺旋体的形成.
- 使用富里埃变换红外 (FTIR) 光谱,核磁共振 (NMR) 和电子循环二元化 (ECD) 的溶液状态分析.
- 高分辨率的X射线晶体学和理论计算以合理化形状偏好.
主要成果:
- 在2.5螺旋结构中容纳了三种新的替代模式.
- 短寡合体中的螺旋性尿素骨干表现出对残留物替代模式的敏感性,包括位置和立体化学.
- 特定的单元,如trans-1,2-diaminocyclohexane,破坏了螺旋核,而cis异构体没有.
结论:
- 形藻的螺旋结构对残留物替代和立体化学的变化敏感.
- 了解这些敏感性对于设计具有控制侧链排列的功能折叠机至关重要.
- 理论和实验数据提供了关于这些型模仿剂的结构偏好和局限性的见解.
相关概念视频
Structures of Carboxylic Acid Derivatives
Structure of Carboxylic Acid Derivatives
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the unhybridized p...
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the unhybridized p...
Basicity of Heterocyclic Aromatic Amines
Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine having a nitrogen atom as part of an aromatic ring has much less basicity than its corresponding alicyclic counterpart. For this reason, as presented in Figure 1, piperidine (pKb = 2.8) is significantly more basic than pyridine (pKb = 8.8).
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Basicity of Aromatic Amines
The basicity of aromatic amines is much weaker than that of aliphatic amines due to the involvement of the lone pair of electrons over the N atom in resonance with the aryl rings. Generally, the electron-donating ability of any substituents on the aryl ring of aromatic amines increases the basicity of the amine by increasing electron density, and hence the availability of lone pair on the nitrogen. On the other hand, electron-withdrawing functional groups on the aryl ring of amines decrease the...
Structure of Amines
The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which is less than the tetrahedral angle of 109.5°. However, the C–N–H bond angle is slightly larger at 112°, with a carbon–nitrogen bond length of 147 pm. This carbon–nitrogen bond length of of amines is longer than the carbon–oxygen bond of alcohols (143 pm) but shorter than alkanes’ carbon–carbon bond (154 pm). These aspects are illustrated in Figure...
Stability of Substituted Cyclohexanes
This lesson discusses the stability of substituted cyclohexanes with a focus on energies of various conformers and the effect of 1,3-diaxial interactions.
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...


