活性化されていない末端オレフィンのIr-触媒化された分子間分岐選択性アリルC-Hアミデーション
1Department of Chemistry , Columbia University , New York , New York 10027 , United States.
Journal of the American Chemical Society
|February 5, 2019
まとめ
効率的なイリジウム触媒法により,アルケンの分岐位置で選択的C-Hアミデーションが可能である. このアプローチは,酸化性アミデーションのためにダイオキサゾロンを利用し,問題のある再編成なしに多様なアミドを生成します.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- アリルC-H機能化は有機合成における重要な変換である.
- 選択的で効率的なC−Hアミデーションの方法の開発は依然として課題です.
- 既存の方法は,しばしば地域選択性または厳しい反応条件に苦しんでいます.
研究 の 目的:
- アルケンの効率的で分岐選択的な分子間C−Hアミデーションを開発する.
- アリルC−H結合を活性化するためにイリジウム (III) 触媒を用いる.
- ダイオクサゾロンの安全で効果的なニトロイド前駆体としての使用を調査する.
主な方法:
- 末端アルケンのイリジウム (III) 触媒反応とダイオクサゾロン.
- アリル-イリジウム (III) の中間物質の分離と特徴づけ
- 収穫量と地域選択性に対する反応条件の最適化.
主要な成果:
- 分子間選択性アリルC-Hアミデーションが成功しました.
- 末端アルケンの分岐位置に多様なアミドが設置された.
- 良い収穫量と高い地域選択性が得られた.
- 主要なアルリル-イリジウム (III) 中間物質の分離と結晶学的特徴化は,反応経路を確認した.
結論:
- 開発されたIr (III) 触媒化された方法は,枝選択性アリルC-Hアミデーションのための効率的な経路を提供します.
- ダイオクサゾロンをニトロイド前駆体として使用すると,カーティウス型再配置のような望ましくない副作用が避けられます.
- この方法論は,アミド機能を含む複雑な分子を合成するための貴重なツールを提供します.
関連する概念動画
Termination of Translation
27.7K
The large ribosomal subunit has several important structures essential to translation. These include the peptidyl transferase center (PTC) - which is the site where the peptide bond is formed - and a large, internal, water-filled tube through which the nascent polypeptide moves. This latter structure is called the Peptide Exit Tunnel, and it begins at the PTC and spans the body of the large ribosomal subunit. During translation, as the nascent polypeptide chain is synthesized, it passes through...
27.7K
Intermolecular Forces in Solutions
39.4K
The formation of a solution is an example of a spontaneous process, a process that occurs under specified conditions without energy from some external source.
When the strengths of the intermolecular forces of attraction between solute and solvent species in a solution are no different than those present in the separated components, the solution is formed with no accompanying energy change. Such a solution is called an ideal solution. A mixture of ideal gases (or gases such as helium and argon,...
When the strengths of the intermolecular forces of attraction between solute and solvent species in a solution are no different than those present in the separated components, the solution is formed with no accompanying energy change. Such a solution is called an ideal solution. A mixture of ideal gases (or gases such as helium and argon,...
39.4K
Intermolecular Forces
70.8K
Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
70.8K
Intermolecular vs Intramolecular Forces
96.7K
Intermolecular forces (IMF) are electrostatic attractions arising from charge-charge interactions between molecules. The strength of the intermolecular force is influenced by the distance of separation between molecules. The forces significantly affect the interactions in solids and liquids, where the molecules are close together. In gases, IMFs become important only under high-pressure conditions (due to the proximity of gas molecules). Intermolecular forces dictate the physical properties of...
96.7K
Comparing Intermolecular Forces: Melting Point, Boiling Point, and Miscibility
51.3K
Intermolecular forces are attractive forces that exist between molecules. They dictate several bulk properties, such as melting points, boiling points, and solubilities (miscibilities) of substances. Molar mass, molecular shape, and polarity affect the strength of different intermolecular forces, which influence the magnitude of physical properties across a family of molecules.
Temporary attractive forces like dispersion are present in all molecules, whether they are polar or nonpolar. They...
Temporary attractive forces like dispersion are present in all molecules, whether they are polar or nonpolar. They...
51.3K
Preparation of Amides
4.0K
Amides are synthesized by treating carboxylic acids with amines in the presence of dehydrating agents like dicyclohexylcarbodiimide (DCC).
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
4.0K


