相关实验视频

Updated: Jun 12, 2025

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Published on: May 21, 2019

合作性有机硫/氧催化能通过内部球电子穿实现极端-极端交叉

Youngeun Hong¹, Changkyu Park¹, Junseong Jang¹

¹Department of Chemistry, Seoul National University, Seoul 08826, Korea.

Journal of the American Chemical Society

|June 2, 2025

概括

这项研究引入了新的合作催化系统,克服了基极交叉反应 (RPC) 的局限性. 这种新方法可以有效合成多种类型的胺,包括与医学相关的胺.

科学领域:

有机化学
催化剂
合成方法

背景情况:

基极交叉 (RPC) 整合了基极和极化学,但受到氧化还原电位匹配的限制.
在极端和极端路径之间进行转换需要对氧化还原事件进行精确的控制.
现有的方法在复杂的转换中面临范围和选择性的挑战.

研究的目的:

通过新型RPC机制开发一个合作的C ((sp3) -N合平台.
为了使可氧化 (异氧) 胺与氧化活性的合.
在传统的RPC反应中克服外层电子转移的局限性.

主要方法:

使用有机硫催化剂的合作催化系统的开发.
在RPC机制中研究内部球电子转移途径.
用于阐明催化剂功能和反应轨迹的实验和计算研究.
功能组兼容性和化学选择性的证明.

主要成果:

建立了一个新的合作催化平台,将RPC从外层转移到内层.
鉴定了一种有机硫催化剂用于选择性电子穿,防止不必要的氧化.
能够有效地将氧化还原活性与 (异质) 胺结合起来.
该方法显示了广泛的功能组耐受性和高化学选择性.

结论:

开发的有机硫催化系统为二级和三级胺提供了有效的途径.
该策略可合成复杂的,具有医学意义的含化合物.
这项研究扩大了极端交叉反应的范围和适用性.

更多相关视频

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Published on: June 20, 2014

Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions

Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions

Published on: July 17, 2020

相关概念视频

Radical Reactivity: Overview

Radical Reactivity: Overview

Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...

Radical Reactivity: Nucleophilic Radicals

Radical Reactivity: Nucleophilic Radicals

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...

Cycloaddition Reactions: MO Requirements for Photochemical Activation

Cycloaddition Reactions: MO Requirements for Photochemical Activation

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.

Radical Formation: Addition

Radical Formation: Addition

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...

Photochemical Electrocyclic Reactions: Stereochemistry

Photochemical Electrocyclic Reactions: Stereochemistry

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

Radical Anti-Markovnikov Addition to Alkenes: Mechanism

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...