简单的,化学选择性的,催化性烯酸异构化.
Steven W M Crossley1, Francis Barabé, Ryan A Shenvi
1Department of Chemistry, The Scripps Research Institute , La Jolla, California 92037, United States.
Journal of the American Chemical Society
|November 15, 2014
概括
催化剂异构终端和循环二烯. 这些催化剂还可以打开紧张的环,耐受各种功能组,如氨基和环氧化物.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 有机合成 有机合成
背景情况:
- 烯异构化是有机化学中的一个基本的转化.
- 开发高效和有选择性的催化剂,用于基异构化和相关反应至关重要.
- 了解不同功能组的催化剂行为是实际应用的关键.
研究的目的:
- 为了研究Co(Sal(tBu,tBu))Cl与有机酸盐的催化活性,用于基异构化.
- 探索这些催化剂在二烯的循环异构和应变环的逆循环异构中的作用范围.
- 评估催化系统对各种功能组的耐受性.
主要方法:
- 使用复合物,特别是Co ((Sal ((tBu,tBu)) Cl,作为催化剂.
- 使用有机素作为辅助催化剂或激活剂.
- 研究包括终端烯异构化,二烯循环异构化和张力环开放的反应.
主要成果:
- 催化量Co ((Sal ((tBu,tBu))Cl和有机 irreversibly isomerize终端基的一个位置.
- 催化系统成功地影响了二烯的循环异构化.
- 使用相同的催化剂,也实现了张力环的逆循环异体化.
- 催化剂对强的易斯基 (胺基,伊米达) 和不稳定的功能性 (环氧化物) 具有耐受性.
结论:
- Co(Sal(tBu,tBu))Cl与有机基素一起,为基异构化提供了一个有效的催化系统.
- 催化剂系统表现出多功能性,使烯循环异构化和紧张环开放成为可能.
- 观察到的功能组容忍度扩大了这种催化方法的合成效用.
相关概念视频
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
19.2K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
19.2K
Olefin Metathesis Polymerization: Overview
2.8K
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...
2.8K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
13.9K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
13.9K
Hydroboration-Oxidation of Alkenes
13.0K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
13.0K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
4.1K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
4.1K
Thermal Electrocyclic Reactions: Stereochemistry
2.7K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
2.7K


