催化,非激活的亚利法性基与的分子间化
Christo S Sevov1, John F Hartwig
1Division of Chemical Sciences, Lawrence Berkeley National Laboratory, and Department of Chemistry, University of California, Berkeley , California 94720, United States.
Journal of the American Chemical Society
|June 14, 2013
概括
这项研究提出了一种新的金属催化方法,通过将类添加到烯酸中来合成. 反应有效地进行,为有价值的化合物提供一个没有废物的途径.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 在有机化学中,以太的合成至关重要.
- 将金属催化O-H键添加到烯酸中提供了一个原子经济的途径.
- 以前的方法往往缺乏效率或控制.
研究的目的:
- 开发一种新型的分子间金属催化添加的非活化α-olefins的.
- 建立一个催化系统,以高效地合成以太.
- 为了阐明反应机制.
主要方法:
- 使用金属催化剂为O-H键添加α-olefins.
- 使用的和未激活的α-olefins作为原料.
- 进行了涉及动态静止状态的机械学研究.
主要成果:
- 在非激活的α-olefins中实现了醇的分子间添加.
- 证明了以太形成的催化过程.
- 确定了O-H键的氧化添加和olefin插入作为关键步骤.
结论:
- 开发了一种罕见的催化反应,用于从和烯酸中合成.
- 该机制涉及中间体的动态混合物.
- 这种方法提供了对以太的无浪费和立体选择性方法.
相关概念视频
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.
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.
Electrophilic Addition to Alkynes: Hydrohalogenation
Electrophilic addition of hydrogen halides, HX (X = Cl, Br or I) to alkenes forms alkyl halides as per Markovnikov's rule, where the hydrogen gets added to the less substituted carbon of the double bond. Hydrohalogenation of alkynes takes place in a similar manner, with the first addition of HX forming a vinyl halide and the second giving a geminal dihalide.
Reduction of Alkenes: Catalytic Hydrogenation
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 surface of...
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 surface of...
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...
Acid-Catalyzed Dehydration of Alcohols to Alkenes
In a dehydration reaction, a hydroxyl group in an alcohol is eliminated along with the hydrogen from an adjacent carbon. Here, the products are an alkene and a molecule of water. Dehydration of alcohols is generally achieved by heating in the presence of an acid catalyst. While the dehydration of primary alcohols requires high temperatures and acid concentrations, secondary and tertiary alcohols can lose a water molecule under relatively mild conditions.


