生物触媒C−C結合形成反応の開始メカニズムとしての地面状態電子移転
Haigen Fu1,2, Heather Lam1,2, Megan A Emmanuel1
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
Journal of the American Chemical Society
|June 11, 2021
まとめ
研究者はオレフィンとブロモケトンからキラル分子を生成する エンジニアリングされた酵素を用いた新しい生物触媒法を開発しました このアプローチは,新しい炭素-炭素結合の形成のために,代表されていない基底状態の電子転送機構を使用します.
科学分野:
- 生物触媒
- 有機化学
- 酵素工学
背景:
- 酵素工学は非自然な反応メカニズムを通して 合成能力を拡張します
- フラビン依存酵素は重要な生物触媒であるが,その反応機構は十分に研究されていない.
研究 の 目的:
- アルファブロモケトンを用いたオレフィンの新生物触媒的非対称性水酸化を開発する.
- C−C結合形成におけるフラビン生物触媒における基底状態電子移転の有用性を調査する.
主な方法:
- ニコチナミド依存性サイクロヘクサノン還元酵素 (NCR) の製造に4ラウンドのサイト飽和変異を用いた.
- アルファブロモケトンが水素酸化反応の原始素として用いられる.
- フラビン共因子から基底状態の電子移転経由で急激のイニシアチブを調査した.
主要な成果:
- エンジニアリングされたNCR変異は,高いエナチオ選択性を持つベータキラルサイクロペンタノンを生成するためにサイクリングを触媒化した.
- ワイルドタイプのNCRは,激素終結時にステレオ化学的制御による分子間結合を示した.
- 基底状態の電子移転を用いた非自然なC−C結合形成反応を成功裏に実証した.
結論:
- 非自然生物触媒反応を可能にする 有効なメカニズムです
- 酵素工学は非対称な合成のための新しい触媒活動を生み出すことができます.
- この研究は,複雑な分子構築のための生物触媒の範囲を拡大します.
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