ピナコールカップリングによる炭素結合形成のためのプラズマ電気化学
Jian Wang1,2, Necip B Üner3,4, Scott Edwin Dubowsky3
1Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, Illinois 61801, United States.
Journal of the American Chemical Society
|May 5, 2023
まとめ
研究者は,プラズマで生成されたソルバット電子を使用して,ピナコール結合反応のための持続可能で金属のない方法を開発しました. この電気駆動的なアプローチは有機合成で炭素-炭素結合を形成するための よりグリーンな代替手段を提供します.
科学分野:
- 有機化学
- プラズマ化学
- 持続可能な合成
背景:
- アルデヒドとケトンのピナコール結合には,伝統的に強い還元剤,しばしばステキオメトリックおよび金属ベースの物質が必要です.
- 既存の方法は持続可能性,廃棄物発生,厳しい反応条件の課題に直面しています.
研究 の 目的:
- プラズマ液体プロセスで生成されたソルバット電子を,ピナコール結合のための新しい還元剤として使用することを調査する.
- 還元性有機反応のための金属のない,電気で動いている,そして持続可能な代替案を探求する.
主な方法:
- プラズマ-液体インターフェースを使用して,ソルバット電子の生成.
- メチル-4-ホルミルベンゾアートのパラメトリック研究で,選択性を最適化する.
- 様々なアルデヒドおよびケトン (ベンザルデヒド,ベンジルケトン,フルフラル) との汎用性の実証
- 反応-拡散モデルの開発と,そのメカニズムの解明のためのアビニシオ計算.
主要な成果:
- プラズマで生成されたソルバット電子を用いてピナコール結合を成功させた.
- 大量輸送の管理によってアルコール減少に対する選択性が制御された.
- この方法は,さまざまなカルボニル化合物に対して広範な適用性を示した.
- 反応運動とメカニズムはモデリングと計算研究によって説明されました.
結論:
- プラズマで生成されたソルバット電子は,金属のないピナコール結合の有効で持続的な経路を提供します.
- このアプローチは,還元性有機合成のための有望な電気駆動方法を提供します.
- 反応パラメータ,特に大量輸送の注意深い制御は,高い選択性を達成するために不可欠です.
さらに関連する動画
![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)
関連する概念動画
01:27Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview
1.8K
Wilhelm Rudolph Fittig discovered the pinacol coupling reaction in 1859. It is a radical dimerization reaction and involves the reductive coupling of aldehydes or ketones in the presence of hydrocarbon solvent to yield vicinal diols.
1.8K
01:22Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)
1.1K
Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
1.1K
01:57Preparation of Diols and Pinacol Rearrangement
3.5K
Compounds bearing two hydroxyl groups are known as diols. When the hydroxyl groups are located on adjacent carbon atoms, the diols are called vicinal diols or glycols. Under acidic conditions, vicinal diols undergo a specific reaction called pinacol rearrangement.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
3.5K
01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.9K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.9K
01:20Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)
1.1K
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
1.1K
01:26Thermal and Photochemical Electrocyclic Reactions: Overview
2.4K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
2.4K