一种温和的,催化方法用于脱化基化物:合成和机械学研究
Alex C Bissember1, Anna Levina, Gregory C Fu
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Journal of the American Chemical Society
|August 22, 2012
概括
这项研究利用β-化物消除进行催化脱化,在室温下从基化物有效地产生终端烯酸. 这种新的方法已经成功地应用于合成 (R) - 甲基.
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:
- 催化交叉合反应是有机合成的基础.
- 在这种过程中,β-化物消除往往是不良的副作用.
- 合成终端烯酸的高效方法非常受欢迎.
研究的目的:
- 开发一种新的催化方法来脱化基化物.
- 为了利用通常不需要的β-化物消除步骤作为关键转换.
- 在正式的总合成中展示该方法的实用性,并阐明其机制.
主要方法:
- 使用素连接体对基化物进行催化脱化.
- 开发的方法应用于合成R-mevalonolactone的应用.
- 机制性调查以确定确定速率的步骤,并确定关键的中间体.
主要成果:
- 反应在室温下以优异的产量进行.
- 该方法对各种功能组具有宽容性.
- 机械研究表明,速率决定的步骤是基质依赖的,L(2) PdHBr不是中间体.
结论:
- 开发了一种新且高效的催化脱化基化物到终端烯酸的脱化.
- 该方法为氨酸合成提供了一条实用的途径,并通过正式的总合成得到了验证.
- 机械学的见解提供了对催化反应通路的更深入的理解.
相关概念视频
Radical Substitution: Allylic Bromination
In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
Halogenation of Alkenes
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy radical...
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy radical...
Radical Anti-Markovnikov Addition to Alkenes: Overview
The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.
Formation of Halohydrin from Alkenes
An alkene, such as propene, reacts with bromine in the presence of water to yield a halohydrin. Halohydrins contain a halogen and a hydroxyl group attached to adjacent carbons. When the halogen is bromine, it is called a bromohydrin, while a chlorohydrin has chlorine as the halogen.
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...

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