通过甲基转化导致乙烯乙烯宏循环的反应途径
1Roger Adams Laboratory, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
Journal of the American Chemical Society
|August 18, 2005
概括
这项研究揭示了催化基因转化形成乙烯乙烯宏循环. 宏循环形成是热力学控制的,循环六合体是最稳定的产物,但dialkylalkyne副产品可以抑制催化剂.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 宏分子科学 宏分子科学
背景情况:
- 基基因转化是一个强大的工具,用于碳-碳键的形成.
- 乙烯宏循环的直接合成仍然具有挑战性.
- 催化剂为基转化提供了独特的反应性.
研究的目的:
- 通过基转化,研究通过基转化直接烯乙烯宏循环形成的机制.
- 阐明控制宏观周期大小和稳定的因素.
- 为了确定潜在的催化剂抑制途径.
主要方法:
- 使用催化剂的基转化反应.
- 使用凝透色谱 (GPC) 和MALDI质谱法进行产品分析.
- 可变温度和混杂实验以评估反应可逆性.
主要成果:
- 线性寡合体和大型宏循环的初始形成,然后平衡到最稳定的循环六合体.
- 宏观循环的形成是由热力学控制的,而不是动力学控制的.
- 副产品3-hexyne抑制了催化剂,特别是对于基质.
结论:
- 热力学稳定性决定了催化基因转化中的最终宏循环分布.
- dialkylalkyne的副产品可以捕获催化剂,阻碍arylalkynes的生产性转化.
- 避免或去除基替代基副产品对于有效合成含有基的宏循环至关重要.
相关概念视频
Free-Radical Chain Reaction and Polymerization of Alkenes
The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Preparation of Alkynes: Dehydrohalogenation
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
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: 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...


