Ag-Catalyzed Regiodivergent C-H アミネーションにおける触媒制御された選択性の起源
Yue Fu1, Emily E Zerull2, Jennifer M Schomaker2
1Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
Journal of the American Chemical Society
|February 8, 2022
まとめ
この研究は,銀触媒による窒素移転反応が選択的C−Hアミネーションをどのように達成するかを明らかにしている. リガンド効果や前駆体同一性などの要因を理解することで,C-N結合形成における地域選択性を正確に制御することができる.
科学分野:
- 有機金属化学
- カタリシス
- コンピュータ化学
背景:
- 銀触媒による窒素移転 (NT) 反応は,C−H結合からC−N結合を合成するために不可欠である.
- 触媒制御による地域分散機能化を達成するには,選択性を決定する要因の深い理解が必要です.
研究 の 目的:
- シルバー触媒による 窒素移転反応を計算的に調べるため
- C−H アミネーションにおける地域選択性を支配する要因を解明する.
- 触媒と前駆体選択のための合理的なアプローチを開発する.
主な方法:
- Ag触媒によるNT反応の計算研究.
- C-H結合解離エンタルピー (BDE),電荷移転,ステリック反発,および移行状態のリングストレスの分析.
- トランジション状態の幾何学に対する補助リガンドとニトロンの前駆体効果の調査.
主要な成果:
- 協調したH原子移転 (HAT) /C-N結合形成メカニズムが特定されました.
- リガンドと前駆体アイデンティティは,BDEに対する移行状態の感受性,テッダー長さ,および電子効果に大きな影響を与えます.
- 触媒と前駆体選択の予測モデルが確立されました.
結論:
- この研究は,Ag触媒によるNT反応における地域選択性を制御する要因の統一された理解を提供します.
- 地域差のC-Hアミネーションのための合理的な設計戦略が開発され,アリファティックアルコールの誘導体に対して実験的に検証された.
関連する概念動画
02:17Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
14.8K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
14.8K
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.5K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.5K
02:36Regioselectivity and Stereochemistry of Hydroboration
8.5K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.5K
02:34Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
8.7K
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
8.7K
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
8.2K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
8.2K
01:25Radical Anti-Markovnikov Addition to Alkenes: Overview
3.6K
The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.
3.6K