通过胺C-N键激活的Ni-催化碳酸
James A Walker1, Kevin L Vickerman1, Jenna N Humke1
1Department of Chemistry, Iowa State University , Ames, Iowa 50011, United States.
Journal of the American Chemical Society
|July 15, 2017
概括
这项研究引入了一种新的催化反应,用于使用阿里酸皮纳科尔的o-allylbenzamides. 该方法通过激活胺C-N键来有效合成2--2-二-1H--1-.
科学领域:
- 有机化学
- 催化剂
- 合成方法
背景情况:
- 基炭基化是一种有价值的合成转化.
- 传统的方法通常依赖于C-C键激活,这可能是具有挑战性的.
- 胺C-N键激活提供了一个替代途径.
研究的目的:
- 开发一种新的Ni-催化形式的o-基化.
- 作为合合作伙伴使用酸酸.
- 建立合成2--2,3-二-1H--1-的新途径.
主要方法:
- 使用 () 催化剂激活胺C-N键.
- 反应机制涉及氧化添加,插入Ni (II) - 乙烯键和还原性消除.
- 作为基质,使用了多种替代的o-基胺和基酸醇.
主要成果:
- 反应以外选择性进行,产生2--2,3-二-1H--1-.
- 目标产品的产量中等至高 (46-99%).
- 该范围包括多种酸皮纳科尔和替代的基胺.
结论:
- 氨基酸是通过C-N键激活进行基碳酸酶化的有效基质.
- 这种方法为C-C债券激活策略提供了切实可行的替代方案.
- 开发的方法为合成印衍生物提供了一个新的工具.
相关概念视频
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
9.2K
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.
9.2K
Preparation of Alkynes: Alkylation Reaction
12.4K
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
12.4K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.9K
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...
3.9K
Amines to Amides: Acylation of Amines
3.6K
Various carboxylic acid derivatives (such as acid chlorides, esters, and anhydrides) can be used for the acylation of amines to yield amides. The reaction requires two equivalents of amines. The first amine molecule functions as a nucleophile and attacks the carbonyl carbon to produce a tetrahedral intermediate. This is followed by the loss of the leaving group and restoration of the C=O bond.
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
3.6K
Reduction of Alkenes: Catalytic Hydrogenation
14.5K
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...
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...
14.5K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
5.0K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
5.0K


