"伊化物"可以通过立体选择性构建宝石-二甲基cyclopropanes
Tongchang Fang1,2, Peng Zhang1, Chao Liu1,3
1State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, China.
Angewandte Chemie (International ed. in English)
|September 20, 2024
概括
这项研究引入了一种创新的方法,用于使用化制造立体特异性环烯酸. 这种方法可以有效地合成具有高反选择性复杂分子,这对于药物开发至关重要.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 环烯是药品和天然产品中的重要结构动图.
- 循环烯的立体选择性合成,特别是那些具有多个四元中心的循环烯,仍然是有机化学中的一个重大挑战.
研究的目的:
- 开发一种新的模块化策略,用于二博功能化环烯的立体选择性合成.
- 建立一种方法,以高立体控制的循环环内构建具有挑战性的多四元碳中心.
主要方法:
- 使用化物,对烯酸的立体选择性循环化.
- 在合成 gem-diborylcyclopropanes 中采用一种奇拉辅助剂,以达到高的反选择性.
主要成果:
- 关于用化物对烯酸进行立体选择性循环制的第一份报告.
- 成功合成了具有优异的反选择性合性宝石-二博cyclopropanes.
- 在具有优异立体选择性的循环单元中轻松构建多四元碳中心的演示.
结论:
- 开发的方法提供了一个模块化和高效的途径,以立体特异的二博功能化环.
- 在这个循环化反应中,基组对于实现化学选择性和立体选择性都至关重要.
- 这项工作为访问具有精确立体化学控制的复杂环衍生物提供了一个强大的新工具.
相关概念视频
Regioselectivity and Stereochemistry of Hydroboration
8.1K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.1K
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
4.6K
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
4.6K
Hydroboration-Oxidation of Alkenes
8.0K
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.
8.0K
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
3.8K
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.
3.8K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
10.1K
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.
10.1K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
17.9K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
17.9K


