有机催化碳-烯转化酶
Allison K Griffith1, Christine M Vanos, Tristan H Lambert
1Department of Chemistry, Columbia University, New York, New York 10027, United States.
Journal of the American Chemical Society
|November 7, 2012
概括
开发了一种新的催化碳-烯酸甲解酶策略,使用氨酸催化剂,用化物对环烯环开启. 这种方法利用了 [3 + 2] 范式,超越了在转化化学中的传统 [2 + 2] 循环加法模式.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 转化论反应 转化论反应
背景情况:
- 传统的转解策略通常依赖于 [2 + 2] 循环加法机制.
- 开发用于烯酸和碳转化的新催化系统对于合成效率至关重要.
研究的目的:
- 报告一项新的催化碳-烯转化酶策略.
- 为了研究循环烯与化物的环开放转化.
- 为了介绍一个新的 [3 + 2] 范式的转化化学.
主要方法:
- 使用一个简单的氨酸催化剂.
- 采用环开放式的循环烯的转化.
- 循环烯与化物发生反应.
主要成果:
- 成功开发了一种催化碳-烯转化酶.
- 使用氨酸催化剂演示反应.
- 建立一个 [3 + 2] 反应路径.
结论:
- 报告的策略为碳-烯甲基解剖提供了一条新的途径.
- 氨酸催化反应为传统的转化机制提供了替代方案.
- [3 + 2]范式代表了转化化学中的一个重要的概念进步.
相关概念视频
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...
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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...
Hydroboration-Oxidation of Alkenes
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.
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.

