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Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction01:22

Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

2.4K
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.
2.4K
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

2.3K
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.
2.3K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

9.1K
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.
9.1K
Reduction of Alkynes to trans-Alkenes: Sodium in Liquid Ammonia02:10

Reduction of Alkynes to trans-Alkenes: Sodium in Liquid Ammonia

10.8K
Alkynes can be reduced to trans-alkenes using sodium or lithium in liquid ammonia. The reaction, known as dissolving metal reduction, proceeds with an anti addition of hydrogen across the carbon–carbon triple bond to form the trans product. Since ammonia exists as a gas (bp = −33°C) at room temperature, the reaction is carried out at low temperatures using a mixture of dry ice (sublimes at −78°C) and acetone. 
When dissolved in liquid ammonia, an alkali metal, such as sodium,...
10.8K
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement01:24

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

2.9K
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
2.9K
Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

3.1K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
3.1K

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Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes
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催化降解维尼利丁转移反应

Sudipta Pal1, You-Yun Zhou1, Christopher Uyeda1

  • 1Department of Chemistry, Purdue University , West Lafayette, Indiana 47907, United States.

Journal of the American Chemical Society
|August 16, 2017
PubMed
概括

研究人员使用简单的烯和1,1-二烯开发了一种新的催化还原甲cyclopropanation反应. 这种方法有效地合成了有价值的合成中间体 - - 烯cyclopropanes.

科学领域:

  • 有机化学
  • 催化剂
  • 合成方法

背景情况:

  • 甲cyclopropanes是高度紧张的循环化合物,具有显著的合成效用.
  • 它们的合成通常需要专门的试剂或条件.
  • 甲cyclopropanes的固有应变能量超过和环烯的能量.

研究的目的:

  • 开发一种用于合成甲环的新型催化方法.
  • 用随时可用的1,1-二烯作为维尼利丁单位的前体.
  • 探索催化降解甲基环的机制.

主要方法:

  • 使用双核 (Ni) 催化剂促进反应.
  • 使用简单的烯和1,1-二烯作为起始材料.
  • 通过C-Cl氧化添加的Ni2 (?? 乙烯) 中间体的拟议形成.

主要成果:

  • 已成功实现简单烯的催化降解甲基环.
  • 反应提供了有效的甲基烯cyclopropane结构.
  • 双核Ni催化剂通过提出的中间体促进了转化.

结论:

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  • 已经建立了一种新合成途径,以获得甲基烯cyclopropanes.
  • 催化系统提供了一种有效的方法来产生有价值的合成中间体.
  • 涉及Ni2的拟议机制提供了对反应途径的洞察力.