催化无金属合物C-H氨基化
Wei Pin Teh1, Derek C Obenschain1, Blaise M Black1
1Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, United States.
Journal of the American Chemical Society
|September 10, 2020
概括
研究人员使用催化剂开发了无金属氨化. 这种高效的方法将多样化的功能引入到具有高区域选择性的类分子中.
科学领域:
- 有机化学
- 催化剂
- 合成方法
背景情况:
- 选择性C-H键功能化对于复杂分子合成至关重要.
- 将功能引入诸如类的天然产品面临着合成挑战.
研究的目的:
- 开发一种新的无金属方法来化.
- 为了实现无转换的功能区域选择性引入.
主要方法:
- 使用了大量的化合物 (胺,尿素).
- 直接使用硫胺和硫酸盐作为源而无需分离前体.
- 适用于多种类型的类.
主要成果:
- 建立了一个新的无金属催化系统,用于基氨化.
- 在氨酸的氨基化过程中获得了高产量和优异的区域选择性.
- 该方法具有广泛的适用性,包括各种特类的功能化.
结论:
- 这种催化反应为氨化提供了一种高效和选择性的途径.
- 该方法避免了金属催化剂和复杂的前体制备,简化了合成策略.
- 这种转化对自然产品和其他复杂有机分子的功能有价值.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.7K
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...
3.7K
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
Reduction of Alkenes: Catalytic Hydrogenation
13.7K
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
13.7K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
20.2K
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.
20.2K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
4.6K
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...
4.6K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
2.2K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
2.2K


