![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)
1,9-ダイアルコキシアントラセンは, (1) O2 感受性リンカーとして使用されています
Dumitru Arian1, Larisa Kovbasyuk, Andriy Mokhir
1Institute of Inorganic Chemistry, Ruprecht-Karls-University of Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.
Journal of the American Chemical Society
|February 25, 2011
まとめ
研究者らは,高度な分子ツールを作成するための新型のシングレット酸素 (1O2) 敏感リンク器を開発しました. このリンクは,高速で高生産性の反応を可能にし,新しい探査機やケージ化合物の開発を容易にする.
科学分野:
- 有機化学 オーガニック・ケミストリー
- バイオケミストリー バイオケミストリー
- 分子生物学は分子生物学である.
背景:
- シングレット酸素 (1O2) は,生物学的プロセスと光学療法において重要な役割を果たします.
- 1O2の検出と操作のための正確なツールの開発は,生物学的研究と治療応用にとって不可欠です.
研究 の 目的:
- 9,10-dialkoxyanthracene構造に基づく新しい (1) O (((2) 感受性のリンク剤を設計・合成する.
- 生きている哺乳類の細胞でモニタリングするためのフローロゲン探査機を開発する.
- 可視光で活性化された"ケージ"のオリゴデオキシリボヌクレオチドを作り,標的型に核酸を投与する.
主な方法:
- (1) O (((2) 感受性リンカーを組み込んだフォスフォラミドイト構成要素の合成.
- リンカーをニュクレオシド,光染料,コレステリル誘導体を含む様々な分子断片に結合する.
- リンカー経由でテトラクロロフルオルフェルセインとテトラメチルロダミンを結合させることで,フッ化性プローブの準備.
- "ケージ"のオリゴデオキシリボヌクレオチドの構築で,リンクはブロッカー鎖に含まれています.
主要な成果:
- (1) O (((2) に敏感なリンクは, (1) O (((2) に曝露すると,迅速かつ高収量な割れ目を示します.
- 素探査機は,リンカーの割れに (1) O (((2) によって復元される光が消えたことを示し,1O2濃度と相関する.
- 可視光で活性化された"ケージ"のオリゴデオキシリボヌクレオチドは,効率的にケージを解除し,高収量で活性鎖を放出します.
結論:
- 開発された (1) O (((2) 感受性リンクは,感受性プローブと効率的なケージ化合物の作成のための汎用的な構成要素です.
- 素探査機は,生物学的システムにおける (1) O (((2) のリアルタイムモニタリングのための信頼性の高い方法を提供します.
- "ケージ"のオリゴデオキシリボヌクレオチドは,光活性化遺伝子ターゲティングと治療応用のための有望なプラットフォームを提供します.
関連する概念動画
01:12Cycloaddition Reactions: MO Requirements for Photochemical Activation
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
01:11Aryldiazonium Salts to Azo Dyes: Diazo Coupling
The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the para position.
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01:16[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
02:44Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
02:04Oxidation 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.
03:00Preparation of Epoxides
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...