金催化式的环异构化,将西洛克氨酸酶转化为环基氨酸酶
Liming Zhang1, Sergey A Kozmin
1Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois 60637, USA.
Journal of the American Chemical Society
|September 24, 2004
概括
这项研究引入了首次用黄金催化的西洛克酶的循环异构化. 这种高效的反应在温和的条件下产生西洛西环二烯,这对于合成环二烯非常有用.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 循环异构反应对于构建复杂的循环分子至关重要.
- 黄金催化已经成为有机合成中的一个强大的工具.
- 开发新型的催化转化对enynes仍然是一个活跃的研究领域.
研究的目的:
- 报告第一个黄金催化1-siloxy-5-en-1-ynes的循环异构.
- 探索这种新合成方法的范围和局限性.
- 为了阐明反应机制.
主要方法:
- 使用金化物 (AuCl) 作为催化剂.
- 使用温和的反应条件 (20°C,30分钟).
- 描述循环产品和随后的转化过程.
主要成果:
- 从1-siloxy-5-en-1-ynes中有效合成西洛基环二烯.
- 广泛的基质范围证明了循环异构化.
- 已成功地将西洛西环二烯转化为1,2-和1,3-环二烯.
- 假设的新机制涉及1,2-基迁移.
结论:
- 黄金催化使得1-siloxy-5-en-1-ynes的新型循环聚合成为可能.
- 在温和的条件下,反应有效地进行.
- 氧环二烯的中间体提供了获取有价值的环二烯衍生物的途径.
相关概念视频
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.
Preparation of Epoxides
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
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.
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.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.


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