C−H機能化反応における触媒性能に複雑な反応部位トポロジを関連付けるための機械的に導かれたワークフロー
Ryan C Cammarota1, Wenbin Liu2, John Bacsa2
1Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States.
Journal of the American Chemical Society
|January 24, 2022
まとめ
接近可能な固いターゲット (SMART) のための新しい空間的成形は,C-H機能化のための触媒の形を定量化します. これは反応部位選択性の予測を可能にし,化学における触媒設計と機械学習の応用を進める.
科学分野:
- 触媒と反応工学
- 計算式化学と分子設計
- 有機合成と方法論
背景:
- C-H機能化における基質部位選択性の変更は,酵素活性部位を模倣する触媒基板設計に依存する.
- 複雑な反応部位に対する定量的記述子の欠如のために,触媒の3D形から反応結果を予測することは困難である.
- 機械学習アプリケーションには,予測モデリングのための触媒トポロジを記述する数値入力が必要です.
研究 の 目的:
- 触媒の反応部位の制約を定量化するために,新しい分子記述子,接近可能な固い標的のための空間的成形 (SMART) を導入する.
- ディロジウム触媒を用いたC-H機能化反応におけるサイト選択性を予測するためにSMART記述子を適用する.
- 触媒のステリック・コンゲージと電離性に基づいたC-H機能化のサイト選択性に関する予測モデルを開発する.
主な方法:
- ディロジウム触媒の反応部位の空間的制約を定量化するためのSMART記述子の開発と適用.
- 1-ブロモ-4-ペンチルベンゼンのC-H機能化は,広範囲にわたるディロジウム触媒を用いたドナー/受容カルベンの中間物質を用いる.
- 多変量線形回帰分析は,ステリックおよび電子的要因を組み込んだサイト選択性モデルを構築する.
主要な成果:
- 最適な末端メチレンサイト選択性は,Rh2 ((S-2-Cl-5-MesTPCP) 4で達成された (30. 9: 1 rr, 14: 1 dr, 87% ee).
- ベンジルC-H機能化に対する好みの増加は,オルトCl置換剤 (Rh2 ((TPCP) 4 ,Rh2 ((S-PTAD) 4 ,Rh2 ((S-TCPTAD)) が欠けている触媒で観察された.
- 25のディロジウム触媒のための直感的なグローバルサイト選択性モデルの開発,反応結果とステリック混雑と電友性を相関させる.
結論:
- SMARTディスクリプタは,触媒トポロジを記述するための定量的な方法を提供し,C-H機能化のサイト選択性の機械学習ベースの予測を容易にする.
- この研究は,基底状態の触媒モデルと移行状態を相関させるためのワークフローを確立し,さまざまな化学的および生物学的システムに適用します.
- このアプローチは,突出の反応部位の特徴を線引きすることによって,対応した反応性と選択性を持つ触媒の設計を可能にします.
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