氧化环胺的olefins与亚齐里丁作为一个多功能途径和含有的异环
1Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.
Journal of the American Chemical Society
|November 20, 2003
概括
新的双循环亚齐里丁通过氧化循环氨基化合成使用NH亚齐里丁和N-bromosuccinimide. 这些多功能化合物为多种类型的pyrrolidine和piperidine异环提供了合成路径.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 亚齐里丁是具有显著合成功效的紧张的三分子异循环.
- 双循环亚齐里丁具有独特的结构特征和反应性.
- 为合成复杂的亚齐里丁支架开发高效的方法至关重要.
研究的目的:
- 开发一种易于制备高反应性[5,3]和[6,3]双循环亚齐里丁的方法.
- 探索这些新型双循环亚齐里丁的合成实用性.
- 为了研究外甲双循环亚齐里丁的稳定性和反应性.
主要方法:
- 使用NH亚齐里丁和N-bromosuccinimide,对olefins进行分子内氧化循环氨基化.
- 合成的双循环亚齐里丁产品的表征.
- 探索后续反应以形成罗利丁和皮佩里丁衍生物.
主要成果:
- 成功有效地制备了 [5,3] 和 [6,3] 双循环亚齐里丁.
- 隔离出惊人的稳定的外甲双循环亚齐里丁.
- 展示了对各种pyrrolidine和piperidine异循环的多功能合成接入.
结论:
- 内部分子氧化循环胺是合成双循环亚齐里丁的有效策略.
- 合成的双循环亚齐里丁作为有价值的中间体,用于异循环合成.
- 这种方法扩大了构建含异环的工具包.
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.
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
Oxidative Cleavage of Alkenes: Ozonolysis
In ozonolysis, ozone is used to cleave a carbon–carbon double bond to form aldehydes and ketones, or carboxylic acids, depending on the work-up.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
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...
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...


