环开放元解聚合反应 (ROMP) 的范围,其中包括1-替代的环丁
Airong Song1, Jae Chul Lee, Kathlyn A Parker
1Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400, USA.
Journal of the American Chemical Society
|July 10, 2010
概括
循环布烯衍生物的二次胺和碳醇 Ester 在环开元化聚合 (ROMP) 中表现出反应性. 计算分析揭示了影响这些聚合反应区域化学和立体化学的因素.
科学领域:
- 聚合物化学 聚合物化学
- 有机金属化学 有机金属化学
- 计算化学计算化学
背景情况:
- 环开元化聚合 (ROMP) 是一种强大的聚合物合成技术.
- 环丁烯衍生物为聚合研究提供了独特的结构特征.
研究的目的:
- 为了研究各种1替代环丁烯衍生物的ROMP反应性.
- 阐明控制ROMP和环开放转化 (ROM) 反应的区域和立体化学的因素.
- 用理论计算分析结果.
主要方法:
- 合成和聚合1替代环丁衍生物 (,胺).
- 从ROMP获得的聚合物的特性.
- 密度函数理论 (DFT) 的计算 (B3LYP/6-31G*和LANL2DZ) 来建模反应机制.
主要成果:
- 1 - 环丁碳酸的二次胺基和1 - 环丁-1-甲醇的基成功经历了ROMP.
- 二次胺产生了具有E-olefin配置的翻译不变聚合物.
- 碳醇产生的立体和区域化学异质聚合物.
- 1-cycloputenecarboxylic酸和三级胺经历ROM,但没有ROMP.
- 计算表明,电荷分布和固体相互作用决定了金属基中间体的区域化学和立体化学.
结论:
- 循环丁烯衍生物的替代模式显著影响它们的ROMP和ROM行为.
- 二次胺是通过ROMP进行受控聚合物合成的有希望的单体.
- 计算方法为这些反应的机制细节提供了宝贵的见解.
相关概念视频
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: 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...
Base-Catalyzed Ring-Opening of Epoxides
Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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.
Cycloaddition Reactions: MO Requirements for Thermal Activation
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