通过动力学分析对催化性缩循环的机械研究
Ryan D Baxter1, John Montgomery
1Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, United States.
Journal of the American Chemical Society
|March 29, 2011
概括
这项研究揭示了催化还原循环机制. 只有当基和化物存在时,才会消耗西兰,这表明一个决定速度的氧化循环化步骤.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 有机合成 有机合成
背景情况:
- 降解循环反应在有机合成中至关重要.
- 催化为形成循环化合物提供了一种多功能方法.
- 了解反应机制是优化合成路径的关键.
研究的目的:
- 为了阐明催化,介导的降解循环的机制. ynals.
- 确定催化循环中涉及的速度决定步骤和中间体.
主要方法:
- 进行了动力学研究,以评估与催化剂,基质和缩剂的反应顺序.
- 在各种反应条件下分析西兰的消耗,为其作用提供了洞察力.
主要成果:
- 循环化反应证明了与和的度相关的第一阶动力学.
- 发现该反应与启动阶段的西兰度相比是零级的.
- 只有当基质中存在基和基功能时,才观察到西兰的消耗.
结论:
- 实验数据与反应通过氧化添加Ni(0) 开始于西兰的机制不一致.
- 一个合理的机制涉及一个速度决定的氧化循环化步骤,形成一个金属循环,随后是用西兰素快速减少.
- 这种机制的理解为进一步开发催化还原循环化策略提供了基础.
相关概念视频
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.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
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...
Nitriles to Amines: LiAlH4 Reduction
Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
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.
Reduction of Alkynes to trans-Alkenes: Sodium in Liquid Ammonia
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, dissociates into a...
When dissolved in liquid ammonia, an alkali metal, such as sodium, dissociates into a...
Preparation of Aldehydes and Ketones from Nitriles and Carboxylic Acids
Although it is possible to reduce a carboxylic acid to an aldehyde, strong reducing agents, like lithium aluminum hydride (LAH), prohibit a controlled reduction, instead causing the generated aldehyde to instantly over-reduce to a primary alcohol.
Reducing carboxylic acid derivatives like acyl chlorides (RCOCl), esters (RCO2R′), and nitriles (RCN) using milder aluminum hydride agents like lithium tri-tert-butoxyaluminum hydride [LiAlH(O-t-Bu)3] and diisobutylaluminum hydride [DIBAL-H] allows...
Reducing carboxylic acid derivatives like acyl chlorides (RCOCl), esters (RCO2R′), and nitriles (RCN) using milder aluminum hydride agents like lithium tri-tert-butoxyaluminum hydride [LiAlH(O-t-Bu)3] and diisobutylaluminum hydride [DIBAL-H] allows...


