铜 ((I) 催化基氨基化酶的机理研究
Radhey S Srivastava1, Nathan R Tarver, Kenneth M Nicholas
1Department of Chemistry, University of Louisiana at Lafayette, Louisiana 70504, USA. rss1805@louisiana.edu
Journal of the American Chemical Society
|November 17, 2007
概括
合成了新的铜 (I) 复合物,并将其确定为铜催化基氨基化反应中的关键中间体. 这些发现阐明了这一重要的有机转化过程的机制和区域选择性.
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:
- 铜 (I) 复合物是各种有机转化中的有价值的催化剂.
- 基氨化是形成碳键的关键反应.
- 了解反应中间体是优化催化过程的关键.
研究的目的:
- 为了合成和表征新的铜 (I) 复合物与酸盐联体.
- 为了研究这些复合物的作用,作为铜 (I) 催化基氨化中的中间体.
- 阐明基氨基化反应的机制和区域选择性.
主要方法:
- 铜 (I) 酸盐复合物的合成和表征.
- 对基氨基化反应的固体测量和催化研究.
- 动力学研究,包括哈梅特分析.
- 铜添加物的分离和特征.
- 计算研究 (PM3和DFT) 来建模中间体.
主要成果:
- 合成了新的Cu (I) 复合物,包括[Cu (PhNO) ]PF6 (1) 和[Cu (Et2NPhNO) ]PF6 (2).
- 复合物1被确定为Cu(I) 催化基氨化中的反应性中间体.
- 综合体1表现出阿尔法甲基 styrene 的固态测量区域选择性基胺化.
- 他们分离出了基添加物,[(PhNO) 3Cu (((eta(2) - - 基) ]PF6 (7,8).
- 计算研究支持了拟议的催化中间体和区域选择性.
结论:
- 合成的铜 (I) 复合物是基氨基化中的关键中间体.
- 涉及这些中间体的机制方案解释了观察到的区域选择性.
- 这项研究提供了对铜催化基氨化机制的重要见解.
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...
Radical Substitution: Allylic Bromination
In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
Preparation of Amines: Reductive Amination of Aldehydes and Ketones
Carbonyl compounds and primary amines undergo reductive amination first to produce imines, followed by secondary amines in the same reaction mixture, using selective reducing agents like sodium cyanoborohydride or sodium triacetoxyborohydride. Reductive amination produces different degrees of substitution of amines depending on the starting amine substrate.
Preparation of 1° Amines: Azide Synthesis
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Acid Halides to Ketones: Gilman Reagent
Lithium dialkyl cuprate, also known as Gilman reagents, selectively reduces acid halides to ketones. The acid chloride is treated with Gilman reagent at −78 °C in the presence of ether solution to produce a ketone in good yield.
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen double...
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen double...

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