メタル・オクソ媒介酵素によるアンチ・マルコヴニコフ・アルケンの酸化
Stephan C Hammer1, Grzegorz Kubik1, Ella Watkins1
1Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 210-41, Pasadena, CA 91125, USA.
Science (New York, N.Y.)
|October 14, 2017
まとめ
研究者は,シトクロームP450酵素を効率的なアンチマルコフニコフ酸化のために設計しました. この突破は,オキシゲンを用いてアルケンの原料の選択的酸化を可能にすることで,合成経路を簡素化します.
科学分野:
- 生物触媒
- 有機化学
- 酵素工学
背景:
- アルケンの触媒反マルコフニコフ酸化は,重要な合成課題である.
- サイトクロームP450酵素は多用途の触媒であるが,典型的には他の酸化経路を好む.
研究 の 目的:
- シトクロームP450酵素を設計し, スタイレンの抗マルコフニコフ酸化を触媒化する.
- この困難な化学変換で高い効率と選択性を達成します.
主な方法:
- 誘導進化は,シトクロームP450酵素を改変するために使用されました.
- エンジニアリングされた酵素は,最終的な酸化剤として酸化酸素を使用します.
- このメカニズムは,高エネルギーの中間物質と,水素移動を含むオキシオトランスファーを含みます.
主要な成果:
- エンジニアリングされた酵素は,金属オクソ媒介によるスタイレンのアンチマルコフニコフ酸化を触媒する高効率性を示しています.
- 運動的に好ましいアルケンのエポキシデーションに対するアンチ・マルコヴニコフ酸化の選択性を達成した.
- このプロセスは,エナチオセレクティブの1,2-ヒドリド移行ステップを含みます.
結論:
- エンジニアリングされた P450 サイトクロームは 選択的アルケンの酸化における長年の課題を克服できます
- このアンチ・マルコフニコフ・オキシゲンゼは 価値ある分子への 簡素化された合成経路を提供します
- この酵素は,様々な機能化反応のための合成代謝経路に統合することができる.
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