異なったキラル構造へのゲートウェイとしてのアニオン加速度アミノコップ再配置の新クラス
Isaac Chogii, Pradipta Das, Jason S Fell1
1Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
Journal of the American Chemical Society
|September 9, 2017
まとめ
この研究は,リチウムによる新しいアミノコップ再配置カスケードを導入します. これらの反応は,ステレオ化学的制御のためのキラル補助物質を使用して,複雑なキラル窒素化合物を効率的に生成します.
科学分野:
- 有機化学
- アシンメトリック・シンセシス
- 反応メカニズム
背景:
- アミノ・コップの再編成は,窒素を含む分子を作るのに価値があります.
- これらの再編成における ステレオ化学を制御することは 依然として課題です
研究 の 目的:
- リチウムアシストアシンメトリックアニオン加速度アミノコープ再配置カスケードを開発する.
- この新しい反応のメカニズムと立体化学的制御を調査する.
主な方法:
- 非対称な合成を 制御するためにキラル補助器を 使った
- 反応メカニズムを探求するために密度関数理論 (DFT) を採用した.
- リチウムエノラートのケラ化と,その後のC-CまたはC-X結合の形成を調査した.
主要な成果:
- ワンポット・カスケード反応が成功しました
- DFTが好む段階的な解離再結合メカニズムを特定した.
- コップ製品のステレオ化学を決定する.
- キラルエナミド中間産物とイミン産物の形成を示した.
結論:
- 開発された方法は,複雑なキラル窒素を含むモチーフの迅速かつ予測可能な合成のための堅固な経路を提供します.
- キラル補助体は,前駆体組立,再配置促進,およびステレオ化学的結果において重要な役割を果たします.
- この研究は 価値ある有機分子の非対称合成のためのツールキットを拡張します
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