通过极端-极端交叉对的亚酸化
1Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne EPFL SB ISIC LCSO, BCH 4306 1015 Lausanne Switzerland jerome.waser@epfl.ch.
Chemical science
|September 15, 2023
概括
这项研究引入了一种新方法,用于合成使用高价和基三酸盐的同质酸. 这种光催化过程提供了一条通往有价值的合成构建块的多功能途径.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 光催化作用的光催化
背景情况:
- 在合成复杂的有机分子时,获得同质酸极为重要.
- 现有的亚酸化方法往往缺乏效率或基质范围.
研究的目的:
- 开发一种新且高效的方法来合成同质酸化.
- 为了探索这种转换的光催化回氧-中性激素极性交叉过程.
主要方法:
- 使用高价试剂与基三酸盐结合使用.
- 采用光催化系统来驱动烯的亚齐多-基化.
- 研究一个极端的极性交叉机制.
主要成果:
- 实现了对多种同类propargylic azides的直接访问.
- 对于各种基质,包括具有电子丰富/贫的基,异环和以太替代物的基质,表现出良好的至优异的产量 (34-84%).
- 证实了产品作为多功能构建块的实用性.
结论:
- 开发的光催化酸基化提供了一条高效和多功能途径,以获得同质酸酸.
- 合成的化合物作为pyrroles和生物活性胺的有价值的前体.
- 这种方法扩大了合成有机化学家的工具包.
相关概念视频
Radical Reactivity: Nucleophilic Radicals
2.1K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.1K
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
3.8K
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...
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...
3.8K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
7.8K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
7.8K
Radical Anti-Markovnikov Addition to Alkenes: Overview
3.4K
The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.
3.4K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
5.9K
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.
5.9K
Radical Formation: Addition
1.7K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
1.7K

![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)
