双倒置三明治涉及纳夫他林和环氧三甲烯
Paula L Diaconescu1, Christopher C Cummins
1Department of Chemistry, Room 2-227, Massachusetts Institute of Technology, Cambridge, MA 02139-4307, USA.
Journal of the American Chemical Society
|June 27, 2002
概括
研究人员合成了新的 - 化合物,包括一个 - 桥复合物,K(2)(mu-eta(6),eta(6) - C(10) H(8)) [U(NC[(t) Bu]Mes) ((3) ](2). 这些化合物提供了关于-碳结合和电子结构的见解.
科学领域:
- 有机金属化学 有机金属化学
- 化学 的化学
- 协调化学 协调化学
背景情况:
- 具有庞大的配体的复合物对理解f元素结合有兴趣.
- 之前的研究已经探讨了 - 烯相互作用,但不断寻找新的结构动机.
研究的目的:
- 为了合成和表征新的 - 烯复合物与纳夫他林和环氧八甲烯连接物.
- 研究这些新型化合物的结构和结合性质.
主要方法:
- 通过IU (DME) (NC) (t) Bu (Mes) (3) 与KC (8) 和纳弗反应合成纳弗桥复合物.
- 合成化合物的表征使用X射线结晶学和DFT研究.
- 探索与环氧甲烯的反应,以形成新的-烯复合物.
主要成果:
- 隔离K{2}{mu-eta}{6}{6}{6}{C}{10}H{8}{U}{NC}{t}{Bu}{Mes}{3}{2}在60%的收益率与短的U-C距离.
- 从甲-桥梁前体中形成-环氧甲烯复合物 (M-2-COT和2(2)-mu-COT).
- DFT分析表明,与环氧甲甲烯类似物相比,甲桥复合物中的达结合更强.
结论:
- 已经成功合成了新型的-纳夫他林和-环氧三烯复合物.
- 结构和计算数据提供了对-结合的性质的见解,突出了三角洲相互作用的作用.
- 这项研究扩大了已知的有机活性化物化合物的结构多样性.
相关概念视频
03:37Molecular Shape and Polarity
Dipole Moment of a Molecule
01:57Preparation of Diols and Pinacol Rearrangement
Compounds bearing two hydroxyl groups are known as diols. When the hydroxyl groups are located on adjacent carbon atoms, the diols are called vicinal diols or glycols. Under acidic conditions, vicinal diols undergo a specific reaction called pinacol rearrangement.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
01:13¹H NMR: Complex Splitting
A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
![[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2Ffiles%2Fmedia%2Fscience-education%2Fscience-education-thumbs%2F12422.jpg&w=3840&q=75)
01:21[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
01:13meta-Directing Deactivators: –NO2, –CN, –CHO, –CO2R, –COR, –CO2H
All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for the...
01:28Phase Diagrams of Ternary Systems
Consider a ternary system, which is composed of three components: water (W), ethanoic acid (E), and trichloromethane (T). Here, Ethanoic acid (E) is fully miscible with both water (W) and trichloromethane (T), meaning it can mix entirely with either of them. However, water and trichloromethane have partial miscibility, meaning they can only mix to a certain extent, beyond which two separate phases will form.The phase diagram of a ternary system is represented as an equilateral triangle, where...