サルフォニルヒドラジドは,一般的リドックス中性プラットフォームとして,ラジカルクロスカップリングに使用される
Jiawei Sun1, Áron Péter1, Jiayan He1
1Department of Chemistry, Scripps Research, La Jolla, CA, USA.
Science (New York, N.Y.)
|March 6, 2025
まとめ
サルフォニル水酸化物は,酸化還元中性クロスカップリングを通じてC-C結合形成のための多用途のラジカル前駆体として作用する. これらの反応は効率的で,外部添加物を必要とせず,軽度の後期機能化を可能にします.
科学分野:
- 有機化学
- 合成化学
背景:
- サルフォニル水酸化物は,有機合成における潜在的な応用がある安定化合物である.
- カーボニル化合物の還元性アリレーションは有機化学における重要な変換である.
研究 の 目的:
- サルフォニルヒドラジドが多用途の原始物質としての有用性を実証する.
- サルフォニル水酸化物を用いて効率的なC−C結合形成クロスカップリング反応を開発する.
主な方法:
- リドックス中性クロスカップリング反応において,サルフォニルヒドラジドを原始素として利用する.
- 活性化オレフィン,アルキルハリド,アリルハリドを含む様々な結合パートナーを使用しています.
- 様々なC−C結合を形成する7種類の化合物との反応を研究する.
主要な成果:
- C ((sp3) -C ((sp3)),C ((sp3) -C ((sp2)),C ((sp3) -C ((sp)) を含む7種類のC-C結合形成クロスカップリングを成功裏に達成しました.
- サルフォニルヒドラジドが前駆体と電子ドナーの両方として作用し,外因的酸化還元添加物の必要性を否定することを実証した.
- 均質で,水に適合し,操作的に単純な反応条件を確立した.
結論:
- サルフォニルヒドラジドは,多様なC−C結合形成のための非常に多用途の原始物質である.
- 開発された方法論は,合成と軽度の後期機能化への簡素化されたアプローチを提供します.
- 反応は効率的でレドックス中性であり,外部レドックス媒介体を必要としない.
![[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)
関連する概念動画
02:26Preparation and Reactions of Sulfides
4.7K
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
4.7K
01:33Radical Reactivity: Intramolecular vs Intermolecular
1.7K
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
1.7K
01:16Radical Reactivity: Nucleophilic Radicals
2.0K
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...
2.0K
01:11Radical Reactivity: Overview
2.0K
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...
2.0K
00:54Radical Formation: Homolysis
3.5K
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.
3.5K
01:27Radical Substitution: Allylic Bromination
4.9K
In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
4.9K