レドックス中性条件下におけるサイクロアルカノールの電光化学 Ce-触媒式環開き機能化:範囲とメカニズム
Zhaoliang Yang1, Dali Yang1, Jianye Zhang2
1The Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, P. R. China.
Journal of the American Chemical Society
|July 21, 2022
まとめ
この研究は,サイクロアルカノールにおける選択的なC−C結合分裂のための新しい電光化学セリウム触媒法を示している. このリドックス中性アプローチは,有機合成とバイオマスの変換のための持続可能な経路を提供することで,多様な機能性を可能にします.
科学分野:
- 有機化学
- カタリシス
- 持続可能な化学
背景:
- アルコールにおける選択的C−C結合分裂は,有機合成とバイオマス変換に不可欠である.
- 低コストの触媒とクリーンエネルギーを使った 酸化還元中性触媒の方法の開発は 重要な課題です
研究 の 目的:
- サイクロアルカノールのリング開封機能化のための多用途のリドックス中性方法について報告する.
- この変換のための電光化学 (EPC) セリウム (Ce) 触媒を実証する.
主な方法:
- サイクロアルカノールリング開封のための電光化学 (EPC) セリウム触媒を用いた.
- クロライドを対アニオンと電解質として直接機能化に使用する.
- 顕微鏡による特徴づけを用いて,予備的なメカニズム調査を行った.
主要な成果:
- 様々なリングサイズのサイクロアルカノールで選択的なC−C結合分裂を達成した.
- 幅広い機能群に対する耐性を示した.
- C-ハリド結合の代わりに,β分裂によってC-CN,C-C,C-S,またはC-オキシーム結合が成功している.
- 外部酸化物質を避け,セリウム触媒の電気酸化と光還元を含む酸化還元中性触媒サイクルを確立した.
結論:
- 開発されたEPC-Ce触媒は,サイクロアルカノール機能化のための汎用的かつ持続可能な方法を提供します.
- Ce (III) /Ce (IV) 触媒経路は,Ce (IV) 酸化アルコシドの中間物質を含む,観察された変換を支えている.
- このアプローチは,有機合成とバイオマス変換戦略を進めるための大きな希望を持っています.
関連する概念動画
Base-Catalyzed Ring-Opening of Epoxides
8.8K
Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
8.8K
Acid-Catalyzed Ring-Opening of Epoxides
7.6K
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
7.6K
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
2.3K
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
2.3K
Cycloaddition Reactions: Overview
2.7K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
2.7K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
8.0K
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.
8.0K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
6.1K
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.
6.1K


