一个化学选择性极性不匹配的光催化C(sp3 ) -C(sp2 ) 交叉合由协同激活激活
Jeremy Brals1, Thomas M McGuire2, Allan J B Watson1
1EaStCHEM, School of Chemistry, University of St Andrews, Purdie Building, North Haugh, St Andrews, KY16 9ST, UK.
Angewandte Chemie (International ed. in English)
|August 25, 2023
概括
研究人员开发了一种新的C(sp3) -C(sp2) 合反应,使用烯酸和氧化还原活性. 这种光氧催化过程利用一种不寻常的激素添加机制,使选择性化学合成为可能.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 摄影化学的使用.
背景情况:
- 在有机合成中,开发高效的C-C键形成策略至关重要.
- 现有的方法往往缺乏化学选择性或需要特定的反应条件.
- 光反氧催化提供了一个强大的平台,以激素为媒介的转化.
研究的目的:
- 开发一种新的C(sp3) -C(sp2) 合反应.
- 在光反氧催化过程中利用烯酸和氧化还原活性.
- 阐明独特的反应机制及其化学选择性.
主要方法:
- 使用可见光进行光反催化.
- 采用烯酸和N-基胺 (NHPI) Ester作为基质.
- 详细的机制研究,包括激素捕捉和动力学分析.
主要成果:
- 成功开发了一种C ((sp3) -C ((sp2) 合反应.
- 反应通过一种不寻常的极性不匹配的基质加法机制进行.
- 在其他烯受体的存在下,证明了烯酸的化学选择性合.
- 详细的机理性调查显示,激素前体和有机的协同激活.
结论:
- 已经建立了一个新的,高效的光反催化C ((sp3) -C ((sp2) 合反应.
- 独特的机制允许使用现有方法无法实现的化学选择性转换.
- 这项工作扩大了构建复杂有机分子的工具包.
相关概念视频
Regioselectivity and Stereochemistry of Hydroboration
8.2K
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...
8.2K
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.1K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.1K
Photochemical Electrocyclic Reactions: Stereochemistry
1.9K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.9K
Hydroboration-Oxidation of Alkenes
8.4K
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.
8.4K
Cycloaddition Reactions: MO Requirements for Thermal Activation
3.6K
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
3.6K
Thermal Electrocyclic Reactions: Stereochemistry
2.0K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
2.0K
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)

