通过原子抽象在C8的远程C-H氨基化和基化
Goh Sennari1,2, Hiroki Yamagishi1, Richmond Sarpong1
1Department of Chemistry, University of California, Berkeley, California 94720, United States.
Journal of the American Chemical Society
|March 6, 2024
概括
研究人员开发了一种新方法,使用光氧化催化剂在C8功能化. 这种新的方法可以合成复杂的烯衍生物和天然产品,如烯.
科学领域:
- 有机化学
- 合成化学
- 催化剂
背景情况:
- 坎佛是有机合成中一个有价值的性构建块.
- 现有的花功能化方法有其局限性.
- 需要新的策略来有效地实现坎佛的C-H功能.
研究的目的:
- 开发一种用于C8位置的花功能化的新方法.
- 使用光电还原催化剂进行分子内原子抽象.
- 合成复杂的普罗林衍生物和天然产品.
主要方法:
- 使用了来自坎佛的氨基.
- 在光反条件下生成以为中心的基.
- 进行了1,5原子转移以使C8位置功能化.
- 使用C-H氨基化和化反应进行进一步的合成.
主要成果:
- 在C8通过分子内原子抽象成功实现了骨架的功能.
- 合成的拓复杂的衍生物.
- 实现了几种类的总合成.
结论:
- 开发的光还原法为的C8功能化提供了一条新途径.
- 这种策略提供了有效的化学支架.
- 该方法在复杂分子合成中具有广泛的适用性.
相关概念视频
Benzene to Phenol via Cumene: Hock Process
3.2K
The synthesis of phenol from benzene via cumene and cumene hydroperoxide is called the Hock process. First, a Friedel–Crafts alkylation reaction of benzene with propene gives cumene. Then cumene forms cumene hydroperoxide via a radical chain reaction. In the chain initiation step, the benzylic hydrogen is abstracted to give a benzylic radical. In the chain propagation step, the benzylic radical reacts with an oxygen diradical to form a cumene hydroperoxide radical. The cumene...
3.2K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
3.7K
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 halogen to form a...
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 halogen to form a...
3.7K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
7.7K
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.
7.7K
Nucleophilic Aromatic Substitution: Elimination–Addition
4.0K
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...
4.0K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.0K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
18.0K
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
8.4K
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.
8.4K


