高度立体选择性 [2 + 4] 用β电子捐赠组对素和素的取消
Wenlai Xie1, Ziming Li1, Jiaxi Xu1
1State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
Organic letters
|March 22, 2025
概括
这项研究引入了一种新型的光化学反应,用于合成立体选择性转-3,4-二-1,2-氧沙二氧化物. 反应利用埃诺和基二甲基甲,提供无催化剂,高效和温和的合成途径.
科学领域:
- 有机化学 有机化学
- 摄影化学的使用.
- 有机化学化学 有机化学
背景情况:
- 具有β电子捐赠组的阴子表现出zwitterionic共振形式.
- 酸 () 亚甲可以在蓝光照射后产生烯.
研究的目的:
- 开发一种高度刻板选择的转-3,4-二-1,2-氧沙二氧化物合成.
- 调查控制这种新型反应中的立体选择性的机制和关键因素.
主要方法:
- 乙与β电子捐赠组和基因的光化学反应,这些基因来自基 (基) 亚甲.
- 对反应中间体和立体化学结果的分析.
- 探索电子捐赠群的作用和过渡状态动态.
主要成果:
- 通过核友性攻击形成zwitterionic中间体.
- 中介物循环生成具有高立体选择性的转-3,4-二-1,2-氧沙二氧化物.
- 在温和的,无催化剂条件下获得良好的至优秀的产量.
结论:
- 子上的电子捐赠群对于核友性攻击和循环化步骤都至关重要.
- 在循环过渡状态下,立体电子效应和库伦力决定了高立体选择性.
- 描述的方法为有价值的有机化合物提供了一种多功能,高效和原子经济的方法.
相关概念视频
SN2 Reaction: Stereochemistry
In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
Regioselectivity of Electrophilic Additions-Peroxide Effect
In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.
Regioselectivity and Stereochemistry of Hydroboration
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 stereochemistry.
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 stereochemistry.
Regioselective Formation of Enolates
As depicted in the figure below, the unsymmetrical ketones can form two possible enolates: less substituted or more substituted enolates. Usually, the thermodynamic enolates are formed from the more substituted α-carbon atom, while the kinetic enolates are formed faster by deprotonation from the less substituted position. The thermodynamic enolates have lower energy, so they are more stable. But the energy required to form kinetic enolates is less.
α-Alkylation of Ketones via Enolate Ions
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the strong interaction...
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...


![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)