使用基胺的基和基因的分子间耐力型胺化
Joseph Moran1, Serge I Gorelsky, Elena Dimitrijevic
1Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie-Curie, Ottawa, ON, Canada.
Journal of the American Chemical Society
|December 5, 2008
概括
这项研究引入了一种新的Cope型胺化,用于氧胺和不和化合物之间的无金属和无酸反应. 这种方法有效地合成了氧化物和N-基氧胺,扩大了合成可能性.
科学领域:
- 有机化学 有机化学
- 合成方法论 合成方法论
- 催化剂是一种催化剂.
背景情况:
- 胺化反应对于合成含化合物至关重要.
- 现有的方法通常需要恶劣的条件,金属催化剂或强酸.
- 开发更温和,更通用的氨基化协议是非常可取的.
研究的目的:
- 开发一种没有金属和酸的Cope型胺化反应.
- 为了探索氧胺与和的分子间反应.
- 调查这种新合成方法的范围,局限性和机制方面.
主要方法:
- 使用了水性氧胺和各种基/基.
- 采用反应优化和添加剂选 (例如,氨).
- 进行实验研究与密度函数理论 (DFT) 计算一起进行机械洞察.
主要成果:
- 来自基的氧化物和来自压力基的N-基氧胺的高效合成.
- 与维尼拉具有被证明的反应性,产生基于电子性质的分支或线性产品.
- 确定与常见保护组和功能手柄的兼容性.
- DFT分析阐明了质子转移在N-氧化物中间体中的关键作用.
结论:
- 开发的Cope型胺化为合成有价值的含分子提供了一种温和而有效的途径.
- 该反应表现出可预测的与维尼拉烯的区域选择性.
- 机理学理解突出了特定中间体和质子转移步骤的重要性.
相关概念视频
Amines to Alkenes: Cope Elimination
Cope elimination reaction involves the conversion of tertiary amines to alkene using hydrogen peroxide under thermal conditions, as depicted in figure 1.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
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.
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Introduction
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Amines to Alkenes: Hofmann Elimination
Alkenes can be obtained from amines via an E2 elimination. The amine is first converted into a good leaving group, such as a quaternary ammonium salt. This is accomplished by treating the amine with an excess of alkyl halide, which results in a halide salt. Next, the halide salt is transformed into a hydroxide salt that functions as a base to enable elimination.
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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.
Aldehydes and Ketones with Amines: Imine and Enamine Formation Overview
Primary amines react with carbonyl compounds—aldehydes and ketones—to generate imines. Imines consist of a C=N double bond and are named Schiff bases after its discoverer—the German chemist Hugo Schiff. On the other hand, secondary amines react with carbonyl compounds to give enamines. In enamines, the presence of a C=C double bond adjacent to the nitrogen atom leads to the delocalization of the lone pair.


