エンジニアリングされたサイトクロームP450によるステレオダイバーゲント原子移転基のサイクリング
Qi Zhou1, Michael Chin1, Yue Fu2
1Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, CA 93106, USA.
まとめ
研究者達は 細胞染色体P450のような金属酵素を設計し 自由基反応におけるステレオ化学を制御した. この画期的な発見により 精密な非対称な触媒が実現し 複雑な分子を合成する 新しい強力なツールが提供されました
科学分野:
- バイオカタリシスと合成化学
- 酵素工学と 導かれた進化
- アシンメトリックな触媒と急激な反応
背景:
- 酵素は生物触媒の開発に ユニークな反応性を持っています
- 合成化学では,フリーラジカル反応におけるステレオ化学を制御することは困難です.
- 第"列の移行金属は 酸化還元酵素の設計にインスパイアします
研究 の 目的:
- ステレオセレクティブの原子移転ラジカルサイクリングのためにP450を再利用する.
- 精密なステレオ制御のための金属酵素を設計する.
- アシンメトリック・ラジカル反応のための 進化可能なプラットフォームを開発する
主な方法:
- サイトクロームP450の方向転換
- メタロ酵素を設計して 根幹を循環させる
- ハロゲンリバウンド段階でのステレオ制御を調査する.
主要な成果:
- エンジニアリングされた金属酵素は 根本的なプロセスで実質的なステレオ制御を達成しました
- エナチオとダイアステレオディバージェンスの非対称な触媒が実証された.
- P450酵素を非自然的な激素反応に成功させた.
結論:
- 進化可能なメタロ酵素は,中断基を制御するための新しい解決策を提供します.
- このプラットフォームは,非対称的な急性触媒の精密な立体化学を可能にします.
- 再利用された酵素は 複雑な合成変換に 強力なアプローチを提供します
関連する概念動画
Radical Reactivity: Overview
2.2K
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...
2.2K
Radical Reactivity: Steric Effects
2.0K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
Along with electronic...
2.0K
Radical Reactivity: Intramolecular vs Intermolecular
1.8K
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...
1.8K
Photochemical Electrocyclic Reactions: Stereochemistry
1.9K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.9K
Radical Formation: Overview
2.2K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
2.2K
Thermal and Photochemical Electrocyclic Reactions: Overview
2.5K
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.
2.5K


![[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)