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相关概念视频

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.5K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
2.5K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

3.8K
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...
3.8K
Radical Formation: Addition00:47

Radical Formation: Addition

2.1K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
2.1K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction01:22

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
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.5K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.5K
Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview01:27

Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview

2.1K
Wilhelm Rudolph Fittig discovered the pinacol coupling reaction in 1859. It is a radical dimerization reaction and involves the reductive coupling of aldehydes or ketones in the presence of hydrocarbon solvent to yield vicinal diols.
2.1K

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Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
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不对称的Ni-催化基继电减速合器

Xiaofeng Wei1, Wei Shu1, Andrés García-Domínguez1

  • 1Department of Chemistry, University of Zurich, Winterthurerstrasse 190, Zurich, CH 8057, Switzerland.

Journal of the American Chemical Society
|June 30, 2020
PubMed
概括
此摘要是机器生成的。

这项研究引入了一种新的催化不对称的二碳化合物功能化. 这种方法有效地使用具有高立体选择性的可用化物和烯酸来创建合的形结构.

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科学领域:

  • 有机化学
  • 催化剂
  • 不对称的合成

背景情况:

  • 二碳功能化对于合成异质化合物至关重要.
  • 这种转换的催化不对称变体有限.
  • 减少交叉合策略提供了潜在的优势.

研究的目的:

  • 开发一种高效的非对称分子间催化降解二碳功能化.
  • 为了使Csp2-和Csp3-化物同时添加到各种烯酸中.
  • 为了实现高区域和enantioselectivity在合成合的构建块.

主要方法:

  • 使用催化降低二碳功能化方法.
  • 使用随时可用的Csp2和Csp3化物作为电友.
  • 在室温下研究了与乙烯胺,乙烯和酸乙烯的反应.
  • 用于立体控制的在位生成的合基Ni (III) -中间体.

主要成果:

  • 实现了高区域性和选择性二碳功能化.
  • 证明了两种不同的电友在烯之间同时添加.
  • 已成功使用 (l) - ((+)) - 单离子素合性比索克萨林连接物用于立体定义的Csp3-Csp2键形成.
  • 通过不对称的基质继电减小合 (ARRRCs) 展示了化胺的合成.

结论:

  • 介绍了一种新的高效的非对称分子间催化降解二碳功能化.
  • 突出了这种方法的合成实用性,
  • 在没有敏感的有机金属试剂的情况下建立了对立体控制的Csp3-Csp2键形成的新途径.