一种特殊的原子转移方法胜过诺里希II
Fereshte Ghorbani1, Stefan Andrew Harry1, Joseph N Capilato1
1Department of Chemistry, Johns Hopkins University, 3400 N. Charles Street, Baltimore, Maryland 21218, United States.
Journal of the American Chemical Society
|August 14, 2020
概括
这项研究表明,光激发的和直接通过分子间原子转移 (HAT) 选择性C-H化,而不是诺里什抽象. 在这种不寻常的定向HAT过程中,光促进剂会发生化学转化.
科学领域:
- 有机化学
- 摄影化学
- 反应机制
背景情况:
- 和的光激发使得化物中的选择性sp3C-H化.
- 这种转变的确切机制尚不清楚,
- 了解这种机制对于开发新合成方法至关重要.
研究的目的:
- 为了阐明光诱导的C-H化反应机制由和.
- 在这种转变中研究光促进剂的作用.
- 确定未来方法开发的关键参数.
主要方法:
- 运动研究
- 同位素标记实验
- 19F 核磁共振 (NMR) 光谱学
- 电化学研究
- 合成探头
- 计算化学
主要成果:
- 该机制是通过分子间原子转移 (HAT) 进行的,这与诺里希原子抽象的初始假设相反.
- 光促进剂,如,通过化进行化学转化才能有效.
- 已经记录了一种不寻常的定向HAT形式.
结论:
- 这项研究阐明了由光激发的和所导向的化机制.
- 它强调了光促进剂在反应中的关键作用和转化.
- 这些发现对于设计未来的CH功能化策略至关重要.
相关概念视频
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
7.2K
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
7.2K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
20.3K
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.
20.3K
Base-Promoted α-Halogenation of Aldehydes and Ketones
4.0K
α-Halogenation of aldehydes and ketones is a reaction involving the substitution of α hydrogens with halogens in the presence of a base. The reaction begins with the abstraction of α hydrogen by the base to produce a nucleophilic enolate ion. This intermediate undergoes a subsequent nucleophilic substitution with the halogen to produce a monohalogenated carbonyl compound. If the starting substrate has more than one α hydrogen, it is difficult to stop the reaction...
4.0K
Hydroboration-Oxidation of Alkenes
10.6K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
10.6K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
8.8K
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.
8.8K
Electrophilic Addition to Alkynes: Hydrohalogenation
11.1K
Electrophilic addition of hydrogen halides, HX (X = Cl, Br or I) to alkenes forms alkyl halides as per Markovnikov's rule, where the hydrogen gets added to the less substituted carbon of the double bond. Hydrohalogenation of alkynes takes place in a similar manner, with the first addition of HX forming a vinyl halide and the second giving a geminal dihalide.
11.1K


