![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
有機フォトレドックス触媒によるサイト選択性アリルおよびヘテロアリルC-H機能化の予測モデル
Kaila A Margrey1, Joshua B McManus1, Simone Bonazzi2
1Department of Chemistry, University of North Carolina at Chapel Hill , Chapel Hill, North Carolina 27599-3290, United States.
Journal of the American Chemical Society
|July 19, 2017
まとめ
研究者は,アロマティックおよびヘテロアロマティック化合物の直接C-H機能化部位選択性に関する予測モデルを開発した. この進歩は 精密な分子改変によって 新しい薬剤や農薬の設計に役立ちます
科学分野:
- 有機化学
- 薬剤化学
- コンピュータ化学
背景:
- アロマティック化合物の直接的なC-H機能化は,重要な合成戦略である.
- この方法は医薬品,農薬,複雑な分子の開発に不可欠です.
- アリル機能化のための基本的方法を確立しました.
研究 の 目的:
- 直接的なC-H機能化におけるサイト選択性の予測モデルを作成する.
- アリル機能化化学を製薬業界に関連するヘテロアロマティックシステムに拡張する.
- 異なるヘテロサイクルクラスにおけるサイト選択性の一般的な傾向を特定する.
主な方法:
- 場所の選択性を予測するために電子密度計算を使用した.
- 一般的なヘテロアロマティックシステムに予測モデルを適用した.
- 機能化サイト選択性の一般的な傾向を分析し,特定した.
主要な成果:
- 様々なヘテロサイクルにおける直接的なC-H機能化の部位選択性を成功裏に予測した.
- 開発されたモデルの適用性を医薬品関連ヘテロサイクルに実証した.
- 異なるヘテロサイクルクラスにおけるサイト選択性の一貫した傾向を特定した.
結論:
- 電子密度計算は,C−H機能化部位の選択性を予測するための信頼できる方法を提供します.
- 開発されたモデルと特定された傾向は,機能化されたヘテロアロマティック化合物の合理的な設計を容易にする.
- この研究は,薬物発見と農業化学開発における直接的なC-H機能化の応用を進めています.
さらに関連する動画
関連する概念動画
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.9K
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...
3.9K
01:26Photochemical Electrocyclic Reactions: Stereochemistry
2.3K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
2.3K
01:12Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.8K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.8K
02:36Regioselectivity and Stereochemistry of Hydroboration
9.6K
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 stereochemistry.
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 stereochemistry.
9.6K
02:35Regioselectivity of Electrophilic Additions-Peroxide Effect
11.3K
In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.
11.3K
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
9.2K
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.
9.2K