正式 [3 + 2] 循环添加剂的捐赠者-接受者环烯和烯
1Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712, USA.
Journal of the American Chemical Society
|July 3, 2003
概括
捐赠者-接受者环烯与亚烯通过 [3 + 2] 循环添加反应. 这种新的方法有效地利用各种烯类型合成有价值的二烯化合物.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 循环添加反应是有机合成的基础.
- 捐赠者-接受者环胺提供独特的反应性概况.
- 亚烯是化学合成中的多功能构建模块.
研究的目的:
- 为了探索捐赠者-接受者环烯与亚烯的反应性.
- 开发一种新的形式的双极环加法反应 [3 + 2].
- 为了合成2H-3,4-二 Pyrrole衍生物.
主要方法:
- 使用trimethylsilyl trifluoromethanesulfonate (Me3SiOTf) 激活捐赠者-接受者环胺.
- 活性型环烯与各种异性,芳香和α,β不和烯的反应.
- 循环添加产品的分离和表征.
主要成果:
- 反应通过从激活的环胺中产生的反应性中间体进行.
- 烯酸有效地拦截这些中间体在一个正式的 [3 + 2] 循环添加.
- 获得了高产量的合成有用的2H-3,4-dihydropyrrole产品.
结论:
- 用Me3SiOTf激活的捐赠体接受体环烯酸是循环添加反应的有效前体.
- 这种方法为各种2H-3,4-dihydropyrrole结构提供了一个简单的途径.
- 反应表明了具有不同化类的广泛基质范围.
相关概念视频
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.
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
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...
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...
Cycloaddition Reactions: MO Requirements for Thermal Activation
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.


