由性N,N'-二氧化物- (II) 复合物催化不对称的碳烯反应:非常广泛的基质范围
Ke Zheng1, Jian Shi, Xiaohua Liu
1Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, PR China.
Journal of the American Chemical Society
|November 5, 2008
概括
一个新的 (II) -N,N'-二氧化物复合物使高度反选择性碳烯反应成为可能. 这促进了具有优异选择性和产量的有价值的α-基碳化合物的不对称合成.
科学领域:
- 有机化学 有机化学
- 不对称的合成方法
- 催化剂是一种催化剂.
背景情况:
- 对于生物活性分子来说,α-基碳基化合物的不对称合成至关重要.
- 开发高效的催化系统,以对酶选择性碳烯反应,仍然是一个挑战.
研究的目的:
- 开发一种新型的催化系统,用于高度反选择性碳烯反应.
- 为了合成生物相关的α-基碳烯化合物.
主要方法:
- 使用一种新的 ((II) -N,N extprime-dioxide复合物作为催化剂.
- 在温和的条件下,在糖衍生物/糖酸盐和各种基之间进行了碳烯反应.
主要成果:
- 实现了具有非常优异的enantioselectivities (97-99% ee) 的高度enantioselective碳烯反应.
- 耐受广泛的芳香性,异芳香性和异芳香性酸衍生物和酸.
- 获得高产量的产品.
- 即使降低了1mol%的催化剂负荷,也保持了高的反催化剂选择性.
结论:
- 新型的 (II) -N,N extprime-dioxide复合物是不对称的碳烯反应的有效催化剂.
- 这种方法提供了一条高效的途径,以致于以酶体丰富的α-基碳烯化合物.
- 催化系统在温和条件下和低催化剂负载下表现出强度和效率.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
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...
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
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.
SN2 Reaction: Stereochemistry
In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
α-Alkylation of Ketones via Enolate Ions
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the strong interaction...
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
Nitrosation of Enols
The nitrosation reaction is one of the methods of preparing 1,2-diketones. The enol tautomer of the starting ketone reacts with sodium nitrite in hydrochloric acid, generating the 1,2-diketone after hydrolysis.


