通过点击循环和氨酸转化切割合成一个分子魅力手
Paul G Clark1, Erin N Guidry, Wing Yan Chan
1The Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Journal of the American Chemical Society
|February 18, 2010
概括
研究人员合成了一种独特的多链循环聚合物,类似于分子魅力手. 这种新的结构是通过复杂的分子架构的高级聚合和点击化学技术实现的.
科学领域:
- 聚合物化学 聚合物化学
- 超分子化学 超分子化学
- 有机合成 有机合成
背景情况:
- 复杂的聚合物架构对于先进的材料特性至关重要.
- 开发高效的合成多链结构方法仍然是一个挑战.
- 分子魅力手代表了一种新型的相互锁定的聚合物系统.
研究的目的:
- 合成一个具有分子魅力手结构的多链循环聚合物.
- 开发和应用高效的点击化学,用于聚合物循环和净化.
- 描述合成的魅力手复合体,并确认其连锁性质.
主要方法:
- 催化环开转化聚合 (ROMP) 的周期性烯酸.
- 用铜催化的亚酸环添加 (点击循环化) 用于聚合物形成.
- 使用清除树脂来净化循环聚合物.
- 催化环闭转化为相互锁定聚合物碎片.
主要成果:
- 成功合成一个alpha,omega-diazide功能化的聚胺前体.
- 通过点击循环在19%的收益率形成一个循环聚合物.
- 使用化物和基因功能化的清除树脂净化循环聚合物.
- 通过相互锁定聚乙烯碎片构建一个分子魅力手结构.
结论:
- 这项研究证明了一条可行的通往多链循环聚合物的途径.
- 点击化学和ROMP是创建复杂互锁架构的有效工具.
- 合成的分子魅力手代表了一类新的超分子聚合物.
相关概念视频
Olefin Metathesis Polymerization: Overview
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Cycloaddition Reactions: Overview
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Ziegler–Natta Chain-Growth Polymerization: Overview
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta catalyst, high molecular...
Cationic Chain-Growth Polymerization: Mechanism
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...

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