(ヘテロ) アレンの軽度な,フェロセン触媒によるC-Hイミダーションである
Klement Foo1, Eran Sella, Isabelle Thomé
1Department of Chemistry, The Scripps Research Institute , 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
Journal of the American Chemical Society
|March 25, 2014
まとめ
新しい方法により,ペレステル反応剤と基礎金属触媒を用いた直接的なC-Hイミデーションが可能になりました. このプロセスは,サクシニミドを生成し,アニリンに変換することができ,多用途の合成経路を提供します.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 合成方法論 合成方法論
背景:
- 直接的なC-H機能化は,有機合成の重要な分野である.
- 窒素を含むグループを導入するための温和で効率的な方法の開発は,依然として課題です.
研究 の 目的:
- 直接C−Hイマジテーションのための新しい,シンプルな方法について報告する.
- ラジカル生成のための新しいペレステルベースの自己燃焼反応剤を導入する.
主な方法:
- 新しいペレステルベースの自己燃焼反応剤を基にした基礎金属触媒を用いて.
- 軽度な反応条件下で直接C-Hイミデーションを行う.
- 機械学的研究を用いて反応機構を調査する.
主要な成果:
- 様々なアロマティック・システムのC-H誘導を成功させました.
- 反応の範囲は広く,多様な機能群を許容する.
- サクシニミド製品からアニラインへのインシットデプロテクション.
- フェロセンはペレステル分解の電子シャトルとして作用し,サクシニミジル基を生成する.
結論:
- 開発された方法は,直接のC-H imidationのための簡単で汎用的な経路を提供します.
- 反応の温和な条件と機能群の許容性により,非常に適用可能である.
- 機械学的洞察は,ラジカル生成と伝達におけるフェロセンの役割を明らかにします.
関連する概念動画
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
6.9K
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.
6.9K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
2.6K
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...
2.6K
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
2.0K
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
2.0K
Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism
2.0K
Birch reduction uses solvated electrons as reducing agents. The reaction converts benzene to 1,4-cyclohexadiene. The reaction proceeds by the transfer of a single electron to the ring to form a benzene radical anion. This anion is highly basic—it abstracts a proton from the alcohol to form a cyclohexadienyl radical. Another single electron transfer gives the cyclohexadienyl anion. A proton transfer from the alcohol forms 1,4-cyclohexadiene. Since this reduction occurs via radical anion...
2.0K
Nucleophilic Aromatic Substitution: Elimination–Addition
2.9K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
2.9K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
3.1K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic...
3.1K


