可視光活性化イオン対の電荷移転複合体によるチオール媒介のα-アミノ基形成
Keishi Kohara1, Aaron Trowbridge1, Milo A Smith1
1Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, United Kingdom, CB2 1EW.
Journal of the American Chemical Society
|November 11, 2021
まとめ
この研究は,アルファアミノラジカルを生成するための新しい可視光法を導入しています. このアプローチにより,単純な原料から複雑なサイクルアミン構造を効率的に合成することができる.
科学分野:
- 有機化学
- 写真化学
- 合成方法論
背景:
- 可視光光触媒は 穏やかな条件下で新しい合成経路を可能にします
- 電子ドナー-受容体複合体は 独特の反応機構の鍵です
- 複雑な分子の合成には 反応性中間産物の生成のための新しい方法の開発が不可欠です
研究 の 目的:
- アルファアミノラジカルを還元的に生成する新しい方法について報告する.
- 可視光媒介の多成分結合反応を開発する.
- 代替アミノメチルサイクロペンタンを合成する
主な方法:
- アルキル-イミニウムイオンとチオフェノラート間のイオン対電荷伝送複合体の形成.
- 可視光照射で 電荷伝送複合体を活性化する
- 二次アミン,サイクロプロピルアルデヒド,アルケーンを含む多成分結合反応.
主要な成果:
- アルファ-アミノラジカルを成功裏に生成した.
- 置換されたアミノメチルサイクロペンタンのための多成分結合反応の開発.
- 幅広い範囲と操作のシンプルさを実証する.
結論:
- 開発された方法は,過激な生成のための独特の活性化モードを提供します.
- この変換は周期性アミン構造への効率的な経路を提供します.
- 方法論は簡単に入手可能な材料を使用しています.
関連する概念動画
Radical Formation: Homolysis
3.8K
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
3.8K
Radical Reactivity: Nucleophilic Radicals
2.2K
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...
2.2K
Preparation and Reactions of Thiols
6.8K
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
6.8K
Radical Reactivity: Overview
2.2K
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...
2.2K
Radical Formation: Addition
1.9K
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...
1.9K
Radical Formation: Overview
2.3K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
2.3K


![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)