O-トリチルオキシメスへのラジカルクローゼーションによるカルボサイクリング:ディフェニルディセレニドの劇的な効果
Derrick L J Clive1, Mai P Pham, Rajendra Subedi
1Chemistry Department, University of Alberta, Edmonton, Alberta, Canada T6G 2G2. derrick.clive@ualberta.ca
Journal of the American Chemical Society
|February 8, 2007
まとめ
ヨドアルデヒドのO-トリチルオキシムは,過激なサイクル化によって効率的にオキシムを形成する. この反応は,成功した合成のために,リフルーシングテトラヒドロフーラン (THF) の特定の反応剤を使用します.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 合成化学 合成化学とは
- 激進的な反応が起こりました.
背景:
- O-トリチルオキシムは,有機合成における多用途の中間物質である.
- ラジカルサイクライゼーション反応は,サイクリック化合物を形成するための効率的な経路を提供します.
- ヨドアルデヒドは,様々な合成変換における主要な前駆体として機能する.
研究 の 目的:
- 5-および6-イオドアルデヒドから派生したO-トリチルオキシームの根性サイクリングを調査する.
- ラジカルサイクライゼーションを通じてオキシームを生産するための合成方法を確立する.
- この変換を促進する特定の反応剤の有用性を調査する.
主な方法:
- 5-および6-イオドアルデヒドのO-トリチルオキシムをトリビュチルチン水化物 (Bu3SnH) で処理する.
- 1,1'-アゾビス (((サイクロヘキサン炭素ニトリル) を激素イニシアターとして使用する.
- 添加物としてN,N-二イソプロピレチラミン (i-Pr2NEt) とディフェニルディセレニド (PhSeSePh) を含める.
- テトラヒドロフーラン (THF) で反流条件下で実施された反応.
主要な成果:
- ヨドアルデヒド由来O-トリチルオキシメスの根幹サイクリングの成功.
- ターゲットオキシーム製品の形成.
- 指定条件下で反応の有効性を実証する.
結論:
- この研究は,ヨドアルデヒドのO-トリチルオキシムからオキシムを合成するための実行可能な根幹サイクリング方法を示しています.
- THFにおけるBu3SnH,ACCN,i-Pr2NEt,PhSeSePhの組み合わせは,サイクル化を効果的に促進する.
- この方法は,オキシムを含む分子を構築するための合成化学者のツールキットに貴重な追加を提供します.
関連する概念動画
Redox Reactions
Oxidation-reduction or redox reactions involve the transfer of electrons from one molecule or atom to another. When an atom gains an electron, another atom must lose an electron, meaning oxidation and reduction must occur together. Since the redox occurs in pairs, the atom that gets oxidized is also called the reducing agent or reductant, and the atom that is reduced is also called the oxidizing agent or oxidant. A straightforward way to remember the definitions of oxidation and reduction is...
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
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.
Oxidative Cleavage of Alkenes: Ozonolysis
In ozonolysis, ozone is used to cleave a carbon–carbon double bond to form aldehydes and ketones, or carboxylic acids, depending on the work-up.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H
All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for the...
Phase I Reactions: Oxidation of Carbon-Heteroatom and Miscellaneous Systems
Oxidative reactions are pivotal in metabolizing numerous compounds, including pharmaceutical drugs. These reactions often occur in carbon-heteroatom systems, such as carbon-nitrogen, carbon-sulfur, and carbon-oxygen.
In carbon-nitrogen systems, aliphatic and aromatic amines can undergo oxidative reactions. Secondary and tertiary amines, like those found in tricyclic antidepressants, can undergo N-dealkylation, a process that involves the oxidation of the alkyl group. In addition, oxidative...
In carbon-nitrogen systems, aliphatic and aromatic amines can undergo oxidative reactions. Secondary and tertiary amines, like those found in tricyclic antidepressants, can undergo N-dealkylation, a process that involves the oxidation of the alkyl group. In addition, oxidative...


