二分子ホモリチス置換による三次アルコールの四次炭素への迅速かつモジュラーなアクセス
Colin A Gould1, Andria L Pace1, David W C MacMillan1
1Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States.
Journal of the American Chemical Society
|July 20, 2023
まとめ
フォトレドックス触媒と鉄を用いて,三次性アルコールから四次性炭素を合成する. アルコール・ブロミドのクロスカップリングを効率的にするために,ユニークなハロゲン原子転送反応剤を使用し,複雑な分子を作成します.
科学分野:
- 有機化学
- 合成化学
- カタリシス
背景:
- 四次炭素は多くの生物活性分子に不可欠な構造モチーフです.
- 四次炭素を構成する既存の合成方法は限られており,未開発です.
- 三次アルコールは豊富な,安定した,構造的に多様な原料です.
研究 の 目的:
- 三次アルコールから四次炭素を作るための新しい合成方法を開発する.
- アルコール-ブロミドのクロスカップリングのための実用的で効率的なプロトコルを確立する.
- 開発されたメソッドの広範な適用性と合成の有用性を実証する.
主な方法:
- フォトレドックス触媒と鉄介SH2結合の組み合わせを用いる.
- 新しい,還元活性化ハロゲン原子移転 (XAT) 反応剤を使用しています.
- 軽度な反応条件下でブロミド源と三次アルコールを結合する.
主要な成果:
- ステリカル・コンゲステート・カルボン化合物の 合成が成功しました
- 三次元の断片のアルキル化とベンジル化による四次元の産物の形成を証明した.
- 肝臓受容体アゴニストとケトン/エステルからのモジュラー経路の迅速な合成を達成した.
結論:
- 開発された方法は,四次炭素を合成するための強力な新しい戦略を提供します.
- このプロトコルは温和な条件,幅広い基板範囲,そして実用的な有用性を提供します.
- このアプローチは,複合分子合成を容易にする四次中心置換体に対するモジュール制御を可能にします.
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